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Sample records for electron donor-acceptor interactions

  1. Electron Donor Acceptor Interactions. Final Progress Report

    SciTech Connect

    2002-08-16

    The Gordon Research Conference (GRC) on Electron Donor Acceptor Interactions was held at Salve Regina University, Newport, Rhode Island, 8/11-16/02. Emphasis was placed on current unpublished research and discussion of the future target areas in this field.

  2. 2012 ELECTRON DONOR-ACCEPTOR INTERACTIONS GORDON RESEARCH CONFERENCE, AUGUST 5-10, 2012

    SciTech Connect

    McCusker, James

    2012-08-10

    The upcoming incarnation of the Gordon Research Conference on Electron Donor Acceptor Interactions will feature sessions on classic topics including proton-coupled electron transfer, dye-sensitized solar cells, and biological electron transfer, as well as emerging areas such as quantum coherence effects in donor-acceptor interactions, spintronics, and the application of donor-acceptor interactions in chemical synthesis.

  3. Photocurrent generation through electron-exciton interaction at the organic semiconductor donor/acceptor interface.

    PubMed

    Chen, Lijia; Zhang, Qiaoming; Lei, Yanlian; Zhu, Furong; Wu, Bo; Zhang, Ting; Niu, Guoxi; Xiong, Zuhong; Song, Qunliang

    2013-10-21

    In this work, we report our effort to understand the photocurrent generation that is contributed via electron-exciton interaction at the donor/acceptor interface in organic solar cells (OSCs). Donor/acceptor bi-layer heterojunction OSCs, of the indium tin oxide/copper phthalocyanine (CuPc)/fullerene (C60)/molybdenum oxide/Al type, were employed to study the mechanism of photocurrent generation due to the electron-exciton interaction, where CuPc and C60 are the donor and the acceptor, respectively. It is shown that the electron-exciton interaction and the exciton dissociation processes co-exist at the CuPc/C60 interface in OSCs. Compared to conventional donor/acceptor bi-layer OSCs, the cells with the above configuration enable holes to be extracted at the C60 side while electrons can be collected at the CuPc side, resulting in a photocurrent in the reverse direction. The photocurrent thus observed is contributed to primarily by the charge carriers that are generated by the electron-exciton interaction at the CuPc/C60 interface, while charges derived from the exciton dissociation process also exist at the same interface. The mechanism of photocurrent generation due to electron-exciton interaction in the OSCs is further investigated, and it is manifested by the transient photovoltage characteristics and the external quantum efficiency measurements. PMID:24002235

  4. DONOR-ACCEPTOR INTERACTIONS OF NITROGEN*

    PubMed Central

    Kimura, J. E.; Szent-Györgyi, A.

    1969-01-01

    The nitrogen atoms of organic molecules readily enter into donor-acceptor interactions, giving off an electron from their lone pair. Under favorable conditions the acceptor can form free radicals. S and O atoms behave likewise but less intensely. PMID:4306047

  5. 2004 Electron Donor Acceptor Interactions Gordon Conference - August 8-13, 2004

    SciTech Connect

    GUILFORD JONES BOSTON UNIVERSITY PHOTONICS CENTER 8 ST. MARY'S ST BOSTON, MA 02215

    2005-09-14

    The 2004 Gordon Conference on Donor/Acceptor Interactions will take place at Salve Regina University in Newport, Rhode Island on August 8-13, 2004. The conference will be devoted to the consequences of charge interaction and charge motion in molecular and materials systems.

  6. Remarkable Dependence of the Final Charge Separation Efficiency on the Donor-Acceptor Interaction in Photoinduced Electron Transfer.

    PubMed

    Higashino, Tomohiro; Yamada, Tomoki; Yamamoto, Masanori; Furube, Akihiro; Tkachenko, Nikolai V; Miura, Taku; Kobori, Yasuhiro; Jono, Ryota; Yamashita, Koichi; Imahori, Hiroshi

    2016-01-11

    The unprecedented dependence of final charge separation efficiency as a function of donor-acceptor interaction in covalently-linked molecules with a rectilinear rigid oligo-p-xylene bridge has been observed. Optimization of the donor-acceptor electronic coupling remarkably inhibits the undesirable rapid decay of the singlet charge-separated state to the ground state, yielding the final long-lived, triplet charge-separated state with circa 100% efficiency. This finding is extremely useful for the rational design of artificial photosynthesis and organic photovoltaic cells toward efficient solar energy conversion. PMID:26610285

  7. 2010 Electron Donor-Acceptor Interactions Gordon Research Conference, August 8 - 13, 2010.

    SciTech Connect

    Gerald Meyer

    2010-08-18

    The Gordon Research Conference on Electron Donor Acceptor Interactions (GRC EDAI) presents and advances the current frontiers in experimental and theoretical studies of Electron Transfer Processes and Energy Conversion. The fundamental concepts underpinning the field of electron transfer and charge transport phenomena are understood, but fascinating experimental discoveries and novel applications based on charge transfer processes are expanding the discipline. Simultaneously, global challenges for development of viable and economical alternative energy resources, on which many researchers in the field focus their efforts, are now the subject of daily news headlines. Enduring themes of this conference relate to photosynthesis, both natural and artificial, and solar energy conversion. More recent developments include molecular electronics, optical switches, and nanoscale charge transport structures of both natural (biological) and man-made origin. The GRC EDAI is one of the major international meetings advancing this field, and is one of the few scientific meetings where fundamental research in solar energy conversion has a leading voice. The program includes sessions on coupled electron transfers, molecular solar energy conversion, biological and biomimetic systems, spin effects, ultrafast reactions and technical frontiers as well as electron transport in single molecules and devices. In addition to disseminating the latest advances in the field of electron transfer processes, the conference is an excellent forum for scientists from different disciplines to meet and initiate new directions; for scientists from different countries to make contacts; for young scientists to network and establish personal contacts with other young scientists and with established scientists who, otherwise, might not have the time to meet young people. The EDAI GRC also features an interactive atmosphere with lively poster sessions, a few of which are selected for oral presentations.

  8. Aromatic donor-acceptor interactions in non-polar environments.

    PubMed

    Prentice, Giles M; Pascu, Sofia I; Filip, Sorin V; West, Kevin R; Pantoş, G Dan

    2015-05-14

    We have evaluated the strength of aromatic donor-acceptor interactions between dialkyl naphthalenediimide and dialkoxynaphthalene in non-polar environments. (1)H NMR, UV-vis spectroscopy and isothermal titration calorimetry were used to characterise this interaction. We concluded that the strength of donor-acceptor interactions in heptane is sufficient to drive supramolecular assemblies in this and other aliphatic solvents. PMID:25875729

  9. Electron donor-acceptor interaction of 3,4-dimethylaniline with 2,3-dicyano-1,4-naphthoquinone

    NASA Astrophysics Data System (ADS)

    Neelgund, Gururaj M.; Magadum, Subash R.; Budni, M. L.

    2011-01-01

    The electron donor-acceptor (EDA) interaction between 2,3-dicyano-1,4-naphthoquinone (DCNQ) and 3,4-dimethylaniline (3,4-DMA) is studied in chloroform, dichloromethane and 1:1 (v/v) mixture of chloroform and dichloromethane. The rate of formation of the product was measured as a function of time using UV-vis spectrophotometer. The formation constant ( K) and molar extinction coefficient ( ɛ) values for the formation of EDA complex were evaluated in the temperature range of 20-35 °C. The pseudo-first-order rate constant ( k1) and the second-order rate constant ( k2) for the disappearance of EDA complex and for the formation of product were evaluated. The activation parameters (Δ H#, Δ S# and Δ G#) of the reaction were determined by temperature dependence of rate constants using the Arrhenius plots. The effect of relative permittivity of the medium on the reaction is discussed. The observed results indicate that formation of final product proceeds through initial formation of EDA complex as an intermediate. The product of the reaction was purified by column chromatography method and identified as 3-( N-3,4-dimethyl-phenylamino)-2-cyano-1,4-naphthoquinone by elemental analysis, IR and NMR spectroscopy. On the basis of kinetic, analytical and spectroscopic results, a plausible mechanism for the formation of EDA complex and its transformation into product is proposed.

  10. 2008 Electron Donor Acceptor Interactions Gordon Research Conference-August 3-8, 2009

    SciTech Connect

    Malcolm Forbes and Nancy Ryan Gray

    2009-09-19

    The conference presents and advances the current frontiers in experimental and theoretical studies of Electron Transfer and Transport in Molecular and Nano-scale Systems. The program includes sessions on coupled electron transfers, molecular solar energy conversion, biological and biomimetic systems, spin effects, ultrafast reactions and technical frontiers as well as electron transport in single molecules and devices.

  11. Donor-acceptor electron transport mediated by solitons.

    PubMed

    Brizhik, L S; Piette, B M A G; Zakrzewski, W J

    2014-11-01

    We study the long-range electron and energy transfer mediated by solitons in a quasi-one-dimensional molecular chain (conjugated polymer, alpha-helical macromolecule, etc.) weakly bound to a donor and an acceptor. We show that for certain sets of parameter values in such systems an electron, initially located at the donor molecule, can tunnel to the molecular chain, where it becomes self-trapped in a soliton state, and propagates to the opposite end of the chain practically without energy dissipation. Upon reaching the end, the electron can either bounce back and move in the opposite direction or, for suitable parameter values of the system, tunnel to the acceptor. We estimate the energy efficiency of the donor-acceptor electron transport depending on the parameter values. Our calculations show that the soliton mechanism works for the parameter values of polypeptide macromolecules and conjugated polymers. We also investigate the donor-acceptor electron transport in thermalized molecular chains. PMID:25493866

  12. Donor-acceptor electron transport mediated by solitons

    NASA Astrophysics Data System (ADS)

    Brizhik, L. S.; Piette, B. M. A. G.; Zakrzewski, W. J.

    2014-11-01

    We study the long-range electron and energy transfer mediated by solitons in a quasi-one-dimensional molecular chain (conjugated polymer, alpha-helical macromolecule, etc.) weakly bound to a donor and an acceptor. We show that for certain sets of parameter values in such systems an electron, initially located at the donor molecule, can tunnel to the molecular chain, where it becomes self-trapped in a soliton state, and propagates to the opposite end of the chain practically without energy dissipation. Upon reaching the end, the electron can either bounce back and move in the opposite direction or, for suitable parameter values of the system, tunnel to the acceptor. We estimate the energy efficiency of the donor-acceptor electron transport depending on the parameter values. Our calculations show that the soliton mechanism works for the parameter values of polypeptide macromolecules and conjugated polymers. We also investigate the donor-acceptor electron transport in thermalized molecular chains.

  13. Rational design of aggregation-induced emission luminogen with weak electron donor-acceptor interaction to achieve highly efficient undoped bilayer OLEDs.

    PubMed

    Chen, Long; Jiang, Yibin; Nie, Han; Hu, Rongrong; Kwok, Hoi Sing; Huang, Fei; Qin, Anjun; Zhao, Zujin; Tang, Ben Zhong

    2014-10-01

    In this work, two tailored luminogens (TPE-NB and TPE-PNPB) consisting of tetraphenylethene (TPE), diphenylamino, and dimesitylboryl as a π-conjugated linkage, electron donor, and electron acceptor, respectively, are synthesized and characterized. Their thermal stabilities, photophysical properties, solvachromism, fluorescence decays, electronic structures, electrochemical behaviors, and electroluminescence (EL) properties are investigated systematically, and the impacts of electron donor-acceptor (D-A) interaction on optoelectronic properties are discussed. Due to the presence of a TPE unit, both luminogens show aggregation-induced emission, but strong D-A interaction causes a decrease in emission efficiency and red-shifts in photoluminescence and EL emissions. The luminogen, TPE-PNPB, with a weak D-A interaction fluoresces strongly in solid film with a high fluorescence quantum yield of 94%. The trilayer OLED [ITO/NPB (60 nm)/TPE-PNPB (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm)] utilizing TPE-PNPB as a light emitter shows a peak luminance of 49 993 cd m(-2) and high EL efficiencies up to 15.7 cd A(-1), 12.9 lm W(-1), and 5.12%. The bilayer OLED [ITO/TPE-PNPB (80 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm)] adopting TPE-PNPB as a light emitter and hole transporter simultaneously affords even better EL efficiencies of 16.2 cd A(-1), 14.4 lm W(-1), and 5.35% in ambient air, revealing that TPE-PNPB is an eximious p-type light emitter. PMID:25254940

  14. Spectral engineering in π-conjugated polymers with intramolecular donor-acceptor interactions.

    PubMed

    Beaujuge, Pierre M; Amb, Chad M; Reynolds, John R

    2010-11-16

    With the development of light-harvesting organic materials for solar cell applications and molecular systems with fine-tuned colors for nonemissive electrochromic devices (e.g., smart windows, e-papers), a number of technical challenges remain to be overcome. Over the years, the concept of "spectral engineering" (tailoring the complex interplay between molecular physics and the various optical phenomena occurring across the electromagnetic spectrum) has become increasingly relevant in the field of π-conjugated organic polymers. Within the spectral engineering toolbox, the "donor-acceptor" approach uses alternating electron-rich and electron-deficient moieties along a π-conjugated backbone. This approach has proved especially valuable in the synthesis of dual-band and broadly absorbing chromophores with useful photovoltaic and electrochromic properties. In this Account, we highlight and provide insight into a present controversy surrounding the origin of the dual band of absorption sometimes encountered in semiconducting polymers structured using the "donor-acceptor" approach. Based on empirical evidence, we provide some schematic representations to describe the possible mechanisms governing the evolution of the two-band spectral absorption observed on varying the relative composition of electron-rich and electron-deficient substituents along the π-conjugated backbone. In parallel, we draw attention to the choice of the method employed to estimate and compare the absorption coefficients of polymer chromophores exhibiting distinct repeat unit lengths, and containing various extents of solubilizing side-chains along their backbone. Finally, we discuss the common assumption that "donor-acceptor" systems should have systematically lower absorption coefficients than their "all-donor" counterparts. The proposed models point toward important theoretical parameters which could be further explored at the macromolecular level to help researchers take full advantage of the

  15. Electronic and Chemical Properties of Donor, Acceptor Centers in Graphene.

    PubMed

    Telychko, Mykola; Mutombo, Pingo; Merino, Pablo; Hapala, Prokop; Ondráček, Martin; Bocquet, François C; Sforzini, Jessica; Stetsovych, Oleksandr; Vondráček, Martin; Jelínek, Pavel; Švec, Martin

    2015-09-22

    Chemical doping is one of the most suitable ways of tuning the electronic properties of graphene and a promising candidate for a band gap opening. In this work we report a reliable and tunable method for preparation of high-quality boron and nitrogen co-doped graphene on silicon carbide substrate. We combine experimental (dAFM, STM, XPS, NEXAFS) and theoretical (total energy DFT and simulated STM) studies to analyze the structural, chemical, and electronic properties of the single-atom substitutional dopants in graphene. We show that chemical identification of boron and nitrogen substitutional defects can be achieved in the STM channel due to the quantum interference effect, arising due to the specific electronic structure of nitrogen dopant sites. Chemical reactivity of single boron and nitrogen dopants is analyzed using force-distance spectroscopy by means of dAFM. PMID:26256407

  16. Energy level realignment in weakly interacting donor-acceptor binary molecular networks.

    PubMed

    Zhong, Jian-Qiang; Qin, Xinming; Zhang, Jia-Lin; Kera, Satoshi; Ueno, Nobuo; Wee, Andrew Thye Shen; Yang, Jinlong; Chen, Wei

    2014-02-25

    Understanding the effect of intermolecular and molecule-substrate interactions on molecular electronic states is key to revealing the energy level alignment mechanism at organic-organic heterojunctions or organic-inorganic interfaces. In this paper, we investigate the energy level alignment mechanism in weakly interacting donor-acceptor binary molecular superstructures, comprising copper hexadecafluorophthalocyanine (F16CuPc) intermixed with copper phthalocyanine (CuPc), or manganese phthalocynine (MnPc) on graphite. The molecular electronic structures have been systematically studied by in situ ultraviolet photoelectron spectroscopy (UPS) and low-temperature scanning tunneling microscopy/spectroscopy (LT-STM/STS) experiments and corroborated by density functional theory (DFT) calculations. As demonstrated by the UPS and LT-STM/STS measurements, the observed unusual energy level realignment (i.e., a large downward shift in donor HOMO level and a corresponding small upward shift in acceptor HOMO level) in the CuPc-F16CuPc binary superstructures originates from the balance between intermolecular and molecule-substrate interactions. The enhanced intermolecular interactions through the hydrogen bonding between neighboring CuPc and F16CuPc can stabilize the binary superstructures and modify the local molecular electronic states. The obvious molecular energy level shift was explained by gap-state-mediated interfacial charge transfer. PMID:24433044

  17. Fresh look at electron-transfer mechanisms via the donor/acceptor bindings in the critical encounter complex.

    PubMed

    Rosokha, Sergiy V; Kochi, Jay K

    2008-05-01

    Seminal insights provided by the iconic R. S. Mulliken and his "charge-transfer" theory, H. Taube and his "outer/inner-sphere" mechanisms, R. A. Marcus and his "two-state non-adiabatic" theory, and N. S. Hush and his "intervalence" theory are each separately woven into the rich panoramic tapestry constituting chemical research into electron-transfer dynamics, and its mechanistic dominance for the past half century and more. In this Account, we illustrate how the simultaneous melding of all four key concepts allows sharp focus on the charge-transfer character of the critical encounter complex to evoke the latent facet of traditional electron-transfer mechanisms. To this end, we exploit the intervalence (electronic) transition that invariably accompanies the diffusive encounter of electron-rich organic donors (D) with electron-poor acceptors (A) as the experimental harbinger of the collision complex, which is then actually isolated and X-ray crystallographically established as loosely bound pi-stacked pairs of various aromatic and olefinic donor/acceptor dyads with uniform interplanar separations of r(DA) = 3.1 +/- 0.2 A. These X-ray structures, together with the spectral measurements of their intervalence transitions, lead to the pair of important electron-transfer parameters, H(DA) (electronic coupling element) versus lambdaT (reorganization energy), the ratio of which generally defines the odd-electron mobility within such an encounter complex in terms of the resonance stabilization of the donor/acceptor assembly [D, A] as opposed to the reorganization-energy penalty required for its interconversion to the electron-transfer state [D(+*), A(-*)]. We recognize the resonance-stabilization energy relative to the intrinsic activation barrier as the mechanistic binding factor, Q = 2H(DA)/lambdaT, to represent the quantitative measure of the highly variable continuum of inner-sphere/outer-sphere interactions that are possible within various types of precursor complexes

  18. Tuning the Electron Acceptor in Phthalocyanine-Based Electron Donor-Acceptor Conjugates.

    PubMed

    Sekita, Michael; Jiménez, Ángel J; Marcos, M Luisa; Caballero, Esmeralda; Rodríguez-Morgade, M Salomé; Guldi, Dirk M; Torres, Tomás

    2015-12-21

    Zinc phthalocyanines (ZnPc) have been attached to the peri-position of a perylenemonoimide (PMI) and a perylenemonoanhydride (PMA), affording electron donor-acceptor conjugates 1 and 2, respectively. In addition, a perylene-monoimide-monoanhydride (PMIMA) has been connected to a ZnPc through its imido position to yield the ZnPc-PMIMA conjugate 10. The three conjugates have been studied for photoinduced electron transfer. For ZnPc-PMIMA 10, electron transfer occurs upon both ZnPc and PMIMA excitation, giving rise to a long-lived (340 ps) charge-separated state. For ZnPc-PMI 1 and ZnPc-PMA 2, stabilization of the radical ion pair states by using polar media is necessary. In THF, photoexcitation of either ZnPc or PMI/PMA produces charge-separated states with lifetimes of 375 and 163 ps, respectively. PMID:26593778

  19. Donor-acceptor graphene-based hybrid materials facilitating photo-induced electron-transfer reactions.

    PubMed

    Stergiou, Anastasios; Pagona, Georgia; Tagmatarchis, Nikos

    2014-01-01

    Graphene research and in particular the topic of chemical functionalization of graphene has exploded in the last decade. The main aim is to increase the solubility and thereby enhance the processability of the material, which is otherwise insoluble and inapplicable for technological applications when stacked in the form of graphite. To this end, initially, graphite was oxidized under harsh conditions to yield exfoliated graphene oxide sheets that are soluble in aqueous media and amenable to chemical modifications due to the presence of carboxylic acid groups at the edges of the lattice. However, it was obvious that the high-defect framework of graphene oxide cannot be readily utilized in applications that are governed by charge-transfer processes, for example, in solar cells. Alternatively, exfoliated graphene has been applied toward the realization of some donor-acceptor hybrid materials with photo- and/or electro-active components. The main body of research regarding obtaining donor-acceptor hybrid materials based on graphene to facilitate charge-transfer phenomena, which is reviewed here, concerns the incorporation of porphyrins and phthalocyanines onto graphene sheets. Through illustrative schemes, the preparation and most importantly the photophysical properties of such graphene-based ensembles will be described. Important parameters, such as the generation of the charge-separated state upon photoexcitation of the organic electron donor, the lifetimes of the charge-separation and charge-recombination as well as the incident-photon-to-current efficiency value for some donor-acceptor graphene-based hybrids, will be discussed. PMID:25247140

  20. Tuning the electronic coupling in a low-bandgap donor-acceptor copolymer via the placement of side-chains

    SciTech Connect

    Oberhumer, Philipp M.; Huang, Ya-Shih; Massip, Sylvain; Albert-Seifried, Sebastian; Greenham, Neil C.; Hodgkiss, Justin M.; Friend, Richard H.; James, David T.; Kim, Ji-Seon; Tu Guoli; Huck, Wilhelm T. S.; Beljonne, David; Cornil, Jerome

    2011-03-21

    We present a spectroscopic and theoretical investigation of the effect of the presence and position of hexyl side-chains in the novel low-bandgap alternating donor-acceptor copolymer poly[bis-N,N-(4-octylphenyl)-bis-N,N-phenyl-1, 4-phenylenediamine-alt-5,5'-4',7',-di-2-thienyl-2',1',3'-benzothiadiazole] (T8TBT). We use electronic absorption and Raman spectroscopic measurements supported by calculations of chain conformation, electronic transitions, and Raman modes. Using these tools, we find that sterically demanding side-chain configurations induce twisting in the electronic acceptor unit and reduce the electronic interaction with the donor. This leads to a blue-shifted and weakened (partial) charge-transfer absorption band together with a higher photoluminescence efficiency. On the other hand, sterically relaxed side-chain configurations promote coupling between donor and acceptor units and exhibit enhanced absorption at the expense of luminescence efficiency. The possibility of tuning the donor-acceptor character of conjugated polymers by varying the placement of side-chains has very important ramifications for light emitting diode, Laser, display, and photovoltaic device optimization.

  1. Triazole bridges as versatile linkers in electron donor-acceptor conjugates

    PubMed Central

    de Miguel, Gustavo; Wielopolski, Mateusz; Schuster, David I.; Fazio, Michael A; Lee, Olivia P.; Haley, Christopher K.; Ortiz, Angy L.; Echegoyen, Luis; Clark, Timothy; Guldi, Dirk M.

    2011-01-01

    Aromatic triazoles have been frequently used as π-conjugated linkers in intramolecular electron transfer processes. To gain a deeper understanding of the electron mediating function of triazoles, we have synthesized a family of new triazole-based electron donor-acceptor conjugates. We have connected porphyrins and fullerenes through a central triazole moiety – (ZnP-Tri-C60) – each with a single change in their connection through the linker. An extensive photophysical and computational investigation reveals that the electron transfer dynamics – charge separation and charge recombination – in the different ZnP-Tri-C60 conjugates reflect a significant influence of the connectivity at the triazole linker. Except for m4m-ZnP-Tri-C60 17, the conjugates exhibit through-bond electron transfer with varying rate constants. Since the through-bond distance is nearly equal in the ZnP-Tri-C60 conjugates, the variation in charge separation and charge recombination dynamics is mainly associated with the electronic properties of the conjugates, including orbital energies, electron affinity, and the energies of the excited states. The changes of the electronic couplings are, in turn, a consequence of the different connectivity patterns at the triazole moieties. PMID:21702513

  2. High performance weak donor-acceptor polymers in thin film transistors: effect of the acceptor on electronic properties, ambipolar conductivity, mobility, and thermal stability.

    PubMed

    Yuen, Jonathan D; Fan, Jian; Seifter, Jason; Lim, Bogyu; Hufschmid, Ryan; Heeger, Alan J; Wudl, Fred

    2011-12-28

    We have studied the electronic, physical, and transistor properties of a family of donor-acceptor polymers consisting of diketopyrrolopyrrole (DPP) coupled with different accepting companion units in order to determine the effects of donor-acceptor interaction. Using the electronically neutral benzene (B), the weakly accepting benzothiadiazole (BT), and the strongly accepting benzobisthiadiazole (BBT), the accepting strength of the companion unit was systematically modulated. All polymers exhibited excellent transistor performance, with mobilities above 0.1 cm(2)V(-1)s(-1), even exceeding 1 cm(2)V(-1)s(-1) for one of the BBT-containing polymers. We find that the BBT is the strongest acceptor, enabling the BBT-containing polymers to be strongly ambipolar. The BBT moiety also strengthens interchain interactions, which provides higher thermal stability and performance for transistors with BBT-containing polymers as the active layer. PMID:22043809

  3. Triggering Gel Formation and Luminescence through Donor-Acceptor Interactions in a C3 -Symmetric Tris(pyrene) System.

    PubMed

    Lai, Thanh-Loan; Pop, Flavia; Melan, Caroline; Canevet, David; Sallé, Marc; Avarvari, Narcis

    2016-04-18

    Straightforward modulation of the gelation, absorption and luminescent properties of a tris(pyrene) organogelator containing a C3 -symmetric benzene-1,3,5-tricarboxamide central unit functionalized by three 3,3'-diamino-2,2'-bipyridine fragments is achieved through donor-acceptor interactions in the presence of tetracyanoquinodimethane. PMID:26864120

  4. Photoinduced electron transfer across fixed distances in chlorophyll donor-acceptor molecules

    SciTech Connect

    Wasielewski, M.R.; Johnson, D.G.; Svec, W.A.

    1987-06-01

    The primary events of photosynthesis are a series of rapid, unidirectional electron transfer events between donors and acceptors that are positioned in the reaction center protein at precise spatial orientations and distances relative to one another. Recent work suggests that electron transfer rates depend on distance and free energy of reaction in porphyrin-quinone models in which the distance and orientation of the donor relative to the acceptor is highly restricted. Spacer molecules were developed which were used to link chlorophyll donors with either chlorophyll or quinone acceptors to produce models in which the donor-acceptor distance is well-defined. Recent theoretical studies and photochemical hole-burning experiments have suggested that the actual primary event of photosynthesis is the production of an intramolecular charge transfer state involving the two bacteriochlorophyll molecules of the special pair dimer. This possibility was explored with symmetric, fixed distance chlorophyll dimer. The chlorophyll macrocycles share a common vinyl group at the 2-position. This linkage serves to increase the degree of electronic coupling between the macrocycles. This dimer exhibits a remarkable decrease in fluorescence quantum yield as the dielectric constant of the medium in which it is dissolved increases. This decrease is accompanied by a proportional decrease in the lowest excited singlet state lifetime as measured by picosecond fluorescence and absorption. 11 refs., 2 figs.

  5. Theory and computational modeling: Medium reorganization and donor/acceptor coupling in electron transfer processes

    SciTech Connect

    Newton, M.D.; Feldberg, S.W.; Smalley, J.F.

    1998-03-01

    The continuing goal is to convert the rapidly accumulating mechanistic information about electron transfer (et) kinetics (often representable in terms of simple rate constants) into precise tools for fine-tuned control of the kinetics and for design of molecular-based systems which meet specified et characteristics. The present treatment will be limited to the kinetic framework defined by the assumption of transition state theory (TST). The primary objective of this paper is to report recent advances in the theoretical formulation, calculation, and analysis of energetics and electronic coupling pertinent to et in complex molecular aggregates. The control of et kinetics (i.e., enhancing desired processes, while inhibiting others) involves, of course, both system energetics (especially reorganization energies (E{sub r}) and free energy changes ({Delta}G{sup 0})) and electronic coupling of local D and A sites, which for thermal processes is most directly relevant only after the system has reached the appropriate point (or region) along the reaction coordinate (i.e., the transition state). The authors first discuss TST rate constant models, emphasizing genetic features, but also noting some special features arising when metal electrodes are involved. They then turn to a consideration of detailed aspects of medium reorganization and donor/acceptor coupling. With these theoretical tools in hand, they examine the results of recent applications to complex molecular systems using the techniques of computational quantum chemistry and electrostatics, together with detailed analysis of the numerical results and comparison with recent electrochemical kinetic data.

  6. Relationship Between the Structure Parameters of a Solid Body and the Kinetics of Donor-Acceptor Interaction in Heterogeneous Systems

    NASA Astrophysics Data System (ADS)

    Khentov, V. Ya.; Khussein, Kh. Kh.

    2016-05-01

    Interaction of an organic ligand molecule with the surface of a d-metal or of disperse particles of chemical compounds containing covalent bonds in a nonaqueous solvent (direct synthesis of complex compounds) is determined by the structure parameters of the solid body. The relationships of the rate and energy of activation of the donor-acceptor interaction of the metal with the Grüneisen coefficient and the Debye temperature of the metal have been established.

  7. Relationship Between the Structure Parameters of a Solid Body and the Kinetics of Donor-Acceptor Interaction in Heterogeneous Systems

    NASA Astrophysics Data System (ADS)

    Khentov, V. Ya.; Khussein, Kh. Kh.

    2016-06-01

    Interaction of an organic ligand molecule with the surface of a d-metal or of disperse particles of chemical compounds containing covalent bonds in a nonaqueous solvent (direct synthesis of complex compounds) is determined by the structure parameters of the solid body. The relationships of the rate and energy of activation of the donor-acceptor interaction of the metal with the Grüneisen coefficient and the Debye temperature of the metal have been established.

  8. Donor/acceptor chromophores-decorated triazolyl unnatural nucleosides: synthesis, photophysical properties and study of interaction with BSA.

    PubMed

    Bag, Subhendu Sekhar; Talukdar, Sangita; Das, Suman Kalyan; Pradhan, Manoj Kumar; Mukherjee, Soumen

    2016-06-14

    Much effort has been put forth to develop unnatural, stable, hydrophobic base pairs with orthogonal recognition properties and study their effect on DNA duplex stabilisation. Our continuous efforts on the design of fluorescent unnatural biomolecular building blocks lead us to the synthesis of some triazolyl donor/acceptor unnatural nucleosides via an azide-alkyne 1,3-dipolar cycloaddition reaction as a key step, which we want to report herein. We have studied their photophysical properties and found interesting solvatochromic fluorescence for two of the nucleosides. Photophysical interactions among two donor-acceptor β-nucleosides as well as a pair of α/β-nucleosides have also been evaluated. Furthermore, we have exploited one of the fluorescent nucleosides in studying its interaction with BSA with the help of UV-visible and steady state fluorescence techniques. Our design concept is based on the hypothesis that a pair of such donor/acceptor nucleosides might be involved in π-stacking as well as in photophysical interactions, leading to stabilization of the DNA duplex if such nucleosides can be incorporated into short oligonucleotide sequences. Therefore, the designed bases may find application in biophysical studies in the context of DNA. PMID:27181694

  9. Bipyridinium Polymers That Dock Tetrathiafulvalene Guests in Water Driven by Donor-Acceptor and Ion Pair Interactions.

    PubMed

    Zhang, Yun-Chang; Qin, Ying; Wang, Hui; Zhang, Dan-Wei; Yang, Guanyu; Li, Zhan-Ting

    2016-04-01

    Two water-soluble para-xylylene-connected 4,4'-bipyridinium (BIPY(2+) ) polymers have been prepared. UV-Vis absorption, (1) H NMR spectroscopy, and cyclic voltammetry experiments support that in water the BIPY(2+) units in the polymers form stable 1:1 charge-transfer complexes with tetrathiafulvalene (TTF) guests that bear two or four carboxylate groups. These charge-transfer complexes are stabilized by the donor-acceptor interaction between electron-rich TTF and electron-deficient BIPY(2+) units and electrostatic attraction between the dicationic BIPY(2+) units and the anionic carboxylate groups attached to the TTF core. On the basis of UV-Vis experiments, a lower limit to the apparent association constant of the TTF⋅BIPY(2+) complexes of the mixtures, 1.8×10(6)  m(-1) , has been estimated in water. Control experiments reveal substantially reduced binding ability of the neutral TTF di- and tetracarboxylic acids to the BIPY(2+) molecules and polymers. Moreover, the stability of the charge-transfer complexes formed by the BIPY(2+) units of the polymers are considerably higher than that of the complexes formed between two monomeric BIPY(2+) controls and the dicarboxylate-TTF donor; this has been attributed to the mutually strengthened electron-deficient nature of the BIPY(2+) units of the polymers due to the electron-withdrawing effect of the BIPY(2+) units. PMID:26833904

  10. Charge transfer in the electron donor-acceptor complexes of a meso-phenol BODIPY dye with chloranils and fullerenes

    NASA Astrophysics Data System (ADS)

    Karmakar, Animesh; Chaudhuri, Tandrima; Mula, Soumyaditya; Chattopadhyay, Subrata

    2015-02-01

    UV-Vis spectral investigations of electron donor-acceptor complexes of laser dye 2,6-Diethyl-4,4-difluoro-1,3,5,7-tetramethyl-8-(4‧-hydroxyphenyl)-4-bora-3a,4a-diaza-s-indecene (1c) with chloranils and fullerenes are reported in toluene medium. Well defined charge transfer (CT) absorption bands have been located in the visible region. Oscillator strengths, transition dipole and resonance energies of the CT complexes have been estimated. Vertical ionization potential of 1c has been determined utilizing Mulliken's equation. A possible mechanism for the interaction between electronic subsystems of chloranils, [60]- and [70]fullerenes with three different BODIPY dyes (1a, 1b and 1c shown in Fig. 1) have been discussed in comparing the parameters like degree of charge transfer and binding constant in nonpolar toluene. Comparison of 1c complexes is done with DFT/B3LYP/6-31G optimized gas phase geometries.

  11. Modulation of electronic and self-assembly properties of a donor-acceptor-donor-based molecular materials via atomistic approach.

    PubMed

    Dhar, Joydeep; Swathi, K; Karothu, Durga Prasad; Narayan, K S; Patil, Satish

    2015-01-14

    The performance of molecular materials in optoelectronic devices critically depends upon their electronic properties and solid-state structure. In this report, we have synthesized sulfur and selenium based (T4BT and T4BSe) donor-acceptor-donor (D-A-D) organic derivatives in order to understand the structure-property correlation in organic semiconductors by selectively tuning the chalcogen atom. The photophysical properties exhibit a significant alteration upon varying a single atom in the molecular structure. A joint theoretical and experimental investigation suggests that replacing sulfur with selenium significantly reduces the band gap and molar absorption coefficient because of lower electronegativity and ionization potential of selenium. Single-crystal X-ray diffraction analysis showed differences in their solid-state packing and intermolecular interactions. Subsequently, difference in the solid-state packing results variation in self-assembly. Micorstructural changes within these materials are correlated to their electrical resistance variation, investigated by conducting probe atomic force microscopy (CP-AFM) measurements. These results provide useful guidelines to understand the fundamental properties of D-A-D materials prepared by atomistic modulation. PMID:25532139

  12. Three Redox States of a Diradical Acceptor-Donor-Acceptor Triad: Gating the Magnetic Coupling and the Electron Delocalization.

    PubMed

    Souto, Manuel; Lloveras, Vega; Vela, Sergi; Fumanal, Maria; Ratera, Imma; Veciana, Jaume

    2016-06-16

    The diradical acceptor-donor-acceptor triad 1(••), based on two polychlorotriphenylmethyl (PTM) radicals connected through a tetrathiafulvalene(TTF)-vinylene bridge, has been synthesized. The generation of the mixed-valence radical anion, 1(•-), and triradical cation species, 1(•••+), obtained upon electrochemical reduction and oxidation, respectively, was monitored by optical and ESR spectroscopy. Interestingly, the modification of electron delocalization and magnetic coupling was observed when the charged species were generated and the changes have been rationalized by theoretical calculations. PMID:27231856

  13. The electronic structure and second-order nonlinear optical properties of donor-acceptor acetylenes - A detailed investigation of structure-property relationships

    NASA Technical Reports Server (NTRS)

    Stiegman, A. E.; Graham, Eva; Khundkar, Lutfur R.; Perry, Joseph W.; Cheng, L.-T.; Perry, Kelly J.

    1991-01-01

    A series of donor-acceptor acetylene compounds was synthesized in which systematic changes in both the conjugation length and the donor-acceptor strength were made. The effect of these structural changes on the spectroscopic and electronic properties of the molecules and, ultimately, on the measured second-order molecular hyperpolarizabilities (beta) was investigated. It was found that increases in the donor-acceptor strength resulted in increases in the magnitude of beta. For this class of molecules, the increase is dominated by the energy of the intramolecular charge-transfer transition, while factors such as the ground to excited-state dipole moment change and the transition-moment integral are much less important. Increasing the conjugation length from one to two acetylene linkers did not result in an increase in the value of beta; however, beta increased sharply in going from two acetylenes to three. This increase is attributed to the superposition of several nearly isoenergetic excited states.

  14. Tuning the Electronic Coupling and Electron Transfer in Mo2 Donor-Acceptor Systems by Variation of the Bridge Conformation.

    PubMed

    Kang, Mei Ting; Meng, Miao; Tan, Ying Ning; Cheng, Tao; Liu, Chun Y

    2016-02-24

    Assembling two quadruply bonded dimolybdenum units [Mo2 (DAniF)3 ](+) (DAniF=N,N'-di(p-anisyl)formamidinate) with 1,4-naphthalenedicarboxylate and its thiolated derivatives produced three complexes [{Mo2 (DAniF)3 }2 (μ-1,4-O2 CC10 H6 CO2 )], [{Mo2 (DAniF)3 }2 (μ-1,4-OSCC10 H6 COS)], and [{Mo2 (DAniF)3 }2 (μ-1,4-S2 CC10 H6 CS2 )]. In the X-ray structures, the naphthalene bridge deviates from the plane defined by the two Mo-Mo bond vectors with the torsion angle increasing as the chelating atoms of the bridging ligand vary from O to S. The mixed-valent species exhibit intervalence transition absorption bands with high energy and very low intensity. In comparison with the data for the phenylene analogues, the optically determined electronic coupling matrix elements (Hab =258-345 cm(-1) ) are lowered by a factor of two or more, and the electron-transfer rate constants (ket ≈10(11)  s(-1) ) are reduced by about one order of magnitude. These results show that, when the electron-transporting ability of the bridge and electron-donating (electron-accepting) ability of the donor (acceptor) are both variable, the former plays a dominant role in controlling the intramolecular electron transfer. DFT calculations revealed that increasing the torsion angle enlarges the HOMO-LUMO energy gap by elevating the (bridging) ligand-based LUMO energy. Therefore, our experimental results and theoretical analyses verify the superexchange mechanism for electronic coupling and electron transfer. PMID:26807909

  15. Ultrafast electron transfer in all-carbon-based SWCNT-C60 donor-acceptor nanoensembles connected by poly(phenylene-ethynylene) spacers.

    PubMed

    Barrejón, Myriam; Gobeze, Habtom B; Gómez-Escalonilla, María J; Fierro, José Luis G; Zhang, Minfang; Yudasaka, Masako; Iijima, Sumio; D'Souza, Francis; Langa, Fernando

    2016-08-21

    Building all-carbon based functional materials for light energy harvesting applications could be a solution to tackle and reduce environmental carbon output. However, development of such all-carbon based donor-acceptor hybrids and demonstration of photoinduced charge separation in such nanohybrids is a challenge since in these hybrids part of the carbon material should act as an electron donating or accepting photosensitizer while the second part should fulfil the role of an electron acceptor or donor. In the present work, we have successfully addressed this issue by synthesizing covalently linked all-carbon-based donor-acceptor nanoensembles using single-walled carbon nanotubes (SWCNTs) as the donor and C60 as the acceptor. The donor-acceptor entities in the nanoensembles were connected by phenylene-ethynylene spacer units to achieve better electronic communication and to vary the distance between the components. These novel SWCNT-C60 nanoensembles have been characterized by a number of techniques, including TGA, FT-IR, Raman, AFM, absorbance and electrochemical methods. The moderate number of fullerene addends present on the side-walls of the nanotubes largely preserved the electronic structure of the nanotubes. The thermodynamic feasibility of charge separation in these nanoensembles was established using spectral and electrochemical data. Finally, occurrence of ultrafast electron transfer from the excited nanotubes in these donor-acceptor nanohybrids has been established by femtosecond transient absorption studies, signifying their utility in building light energy harvesting devices. PMID:27305145

  16. Ab initio MO based lattice energy for molecular crystals: packing structure of electron donor-acceptor (EDA) complex H 3N-BF 3

    NASA Astrophysics Data System (ADS)

    Ikeda, Tohru; Nagayoshi, Kanade; Kitaura, Kazuo

    2003-03-01

    A computational procedure is proposed for calculating the lattice energy of molecular crystals using the ab initio MO method. Our method does not require any adjustable parameters and provides a general description for various molecular crystals including electron donor-acceptor (EDA) complexes. Using the method, the packing structure of H 3N-BF 3 crystal was optimized at the HF/3-21 + G level and the lattice energy was calculated at the MP2/6-311 + G * level. The calculation reproduced the experimental lattice constants with reasonable accuracy. Moreover, the structural feature of the H 3N-BF 3 crystal was discussed based on the molecular interactions in the crystal.

  17. Electron-Donor-Acceptor (EDA) Complexes Of Aromatic Hydrocarbons With Organic Acceptors In Solution And In The Solid State. A Quantitative FT-IR Investigation.

    NASA Astrophysics Data System (ADS)

    Bruni, Paolo; Giorgini, Elisabetta; Tosi, Giorgio; Zampini, Angela

    1989-12-01

    Liquid phase FT-IR investigation on π-π Electron-Donor-Acceptor (EDA) complexes between arenes and organic acceptors leads to values of formation constants that are in good agreement with the ones from other techniques (UV-Vis and NMR). In addition solid state FT-IR and UV-Vis determinations on the complexes are also reported and discussed.

  18. Donor-Acceptor-Type Semiconducting Polymers Consisting of Benzothiadiazole Derivatives as Electron-Acceptor Units for Organic Photovoltaic Cells.

    PubMed

    Kim, Hee Su; Park, Jong Baek; Kim, Ji-Hoon; Hwang, Do-Hoon

    2015-11-01

    We synthesized two fused pentacyclic donor-acceptor structures, where the two different outer electron rich thiophene (DTPBT) and electron poor benzene (ICTh) moieties are covalently bonded to the central electron-deficient benzothiadiazole core by two nitrogen bridges. These new electron-acceptor DTPBT and ICTh building blocks were copolymerized with fluorene, as the electron donor group, via Suzuki coupling polymerization, to produce two new alternating copolymers, PFDTPBT and PFICTh, respectively. The average molecular weights of the synthesized polymers were determined by GPC. The number-average molecular weights of PFDTPBT and PFICTh were 19,000 (PDI = 2.5) and 20,000 (PDI = 4.0), respectively. The optical bandgap energies of the polymers were measured from their absorption onsets to be 2.15 and 2.55 eV, depending on the polymer structure. The HOMO energy levels of the polymers were determined, by measuring the oxidation onsets of the polymer films by cyclic voltammetry. The measured HOMO energy levels of PFDTPBT and PFICTh were -5.10 and -5.57 eV, respectively. When the polymers were blended with PC71BM, as the active layer for bulk-heterojunction photovoltaic devices, power conversion efficiencies were 2.08% and 0.34%, respectively, under AM 1.5 G (100 mW cm(-2)) conditions. PMID:26726610

  19. Rationally designed donor-acceptor scheme based molecules for applications in opto-electronic devices.

    PubMed

    Subash Sundar, T; Sen, R; Johari, P

    2016-04-01

    Several donor (D)-acceptor (A) based molecules are rationally designed by adopting three different schemes in which the conjugation length, strength of the donor and acceptor moieties, and planarity of the molecules are varied. These variations are made by introducing a π-conjugated linkage unit, terminating the ends of the moieties by different electron donating and accepting functional groups, and fusing the donor and acceptor moieties, respectively. Our DFT and TDDFT based calculations reveal that using the above-mentioned design schemes, the electronic and optical properties of the D-A based molecules can be largely tuned. While introduction of a linkage and fusing of moieties enhance the π-π interaction, addition of electron donating groups (-CH3, -OH, and -NH2) and electron accepting groups (-CF3, -CN, -NO2, and -NH3(+)) varies the strength of the donor and acceptor moieties. These factors lead to modulation of the HOMO and LUMO energy levels and facilitate the engineering of the HOMO-LUMO gap and the optical gap over a wide range of ∼0.7-3.7 eV. Moreover, on the basis of calculated ionization potential and reorganization energy, most of the investigated molecules are predicted to be air stable and to exhibit high electron mobility, with the possibility of the presence of ambipolar characteristics in a few of them. The results of our calculations not only demonstrate the examined molecules to be the potential materials for organic opto-electronic devices, but also establish an understanding of the composition-structure-property correlation, which will provide guidelines for designing and synthesizing new materials of choice. PMID:26972386

  20. Electron and hole polaron accumulation in low-bandgap ambipolar donor-acceptor polymer transistors imaged by infrared microscopy

    NASA Astrophysics Data System (ADS)

    Khatib, O.; Mueller, A. S.; Stinson, H. T.; Yuen, J. D.; Heeger, A. J.; Basov, D. N.

    2014-12-01

    A resurgence in the use of the donor-acceptor approach in synthesizing conjugated polymers has resulted in a family of high-mobility ambipolar systems with exceptionally narrow energy bandgaps below 1 eV. The ability to transport both electrons and holes is critical for device applications such as organic light-emitting diodes and transistors. Infrared spectroscopy offers direct access to the low-energy excitations associated with injected charge carriers. Here we use a diffraction-limited IR microscope to probe the spectroscopic signatures of electron and hole injection in the conduction channel of an organic field-effect transistor based on an ambipolar DA polymer polydiketopyrrolopyrrole-benzobisthiadiazole. We observe distinct polaronic absorptions for both electrons and holes and spatially map the carrier distribution from the source to drain electrodes for both unipolar and ambipolar biasing regimes. For ambipolar device configurations, we observe the spatial evolution of hole-induced to electron-induced polaron absorptions throughout the transport path. Our work provides a platform for combined transport and infrared studies of organic semiconductors on micron length scales relevant to functional devices.

  1. Microscopic simulations of electronic excitations in donor-acceptor heterojunctions of small-molecule based solar cells

    NASA Astrophysics Data System (ADS)

    Baumeier, Bjoern

    2015-03-01

    Fundamental processes involving electronic excitations govern the functionality of molecular materials in which the dynamics of excitons and charges is determined by an interplay of molecular electronic structure and morphological order. To understand, e.g., charge separation and recombination at donor-acceptor heterojunctions in organic solar cells, knowledge about the microscopic details influencing these dynamics in the bulk and across the interface is required. For a set of prototypical heterojunctions of small-molecule donor materials with C60, we employ a hybrid QM/MM approach linking density-functional and many-body Green's functions theory and analyze the charged and neutral electronic excitations therein. We pay special attention the spatially-resolved electron/hole transport levels, as well as the relative energies of Frenkel and charge-transfer excitations at the interface. Finally, we link the molecular architecture of the donor material, its orientation on the fullerene substrate as well as mesoscale order to the solar cell performance.

  2. Photo-initiated multi-step electron transfer in donor-acceptor systems using a novel bi-functionalized perylene chromophore

    NASA Astrophysics Data System (ADS)

    Dyar, Scott M.; Smeigh, Amanda L.; Karlen, Steven D.; Young, Ryan M.; Wasielewski, Michael R.

    2015-06-01

    The excited state and redox properties of a new bi-functional perylene redox chromophore, 2,3-dihydro-1-azabenzo[cd]perylene (DABP), are described. Perylene has been widely used in electron donor-acceptor molecules in fields ranging from artificial photosynthesis to molecular spintronics. However, attaching multiple redox components to perylene to carry out multi-step electron transfer reactions often produces hard to separate regioisomers, which complicate data analysis. The use of DABP provides a strategy to retain the electronic properties of perylene, yet eliminate regioisomers. Ultrafast photo-initiated single- and two-step electron transfer reactions in three linear electron donor-acceptor systems incorporating DABP are described to illustrate its utility.

  3. 5' modification of duplex DNA with a ruthenium electron donor-acceptor pair using solid-phase DNA synthesis

    NASA Technical Reports Server (NTRS)

    Frank, Natia L.; Meade, Thomas J.

    2003-01-01

    Incorporation of metalated nucleosides into DNA through covalent modification is crucial to measurement of thermal electron-transfer rates and the dependence of these rates with structure, distance, and position. Here, we report the first synthesis of an electron donor-acceptor pair of 5' metallonucleosides and their subsequent incorporation into oligonucleotides using solid-phase DNA synthesis techniques. Large-scale syntheses of metal-containing oligonucleotides are achieved using 5' modified phosporamidites containing [Ru(acac)(2)(IMPy)](2+) (acac is acetylacetonato; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (3) and [Ru(bpy)(2)(IMPy)](2+) (bpy is 2,2'-bipyridine; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (4). Duplexes formed with the metal-containing oligonucleotides exhibit thermal stability comparable to the corresponding unmetalated duplexes (T(m) of modified duplex = 49 degrees C vs T(m) of unmodified duplex = 47 degrees C). Electrochemical (3, E(1/2) = -0.04 V vs NHE; 4, E(1/2) = 1.12 V vs NHE), absorption (3, lambda(max) = 568, 369 nm; 4, lambda(max) = 480 nm), and emission (4, lambda(max) = 720 nm, tau = 55 ns, Phi = 1.2 x 10(-)(4)) data for the ruthenium-modified nucleosides and oligonucleotides indicate that incorporation into an oligonucleotide does not perturb the electronic properties of the ruthenium complex or the DNA significantly. In addition, the absence of any change in the emission properties upon metalated duplex formation suggests that the [Ru(bpy)(2)(IMPy)](2+)[Ru(acac)(2)(IMPy)](2+) pair will provide a valuable probe for DNA-mediated electron-transfer studies.

  4. The Tetrathiafulvalene-based Donor-acceptor Diads for Molecular Electronics

    NASA Astrophysics Data System (ADS)

    Perepichka, Dmitrii F.; Bryce, Martin R.; Ho, Gregory; Heath, James R.; Pearson, Christopher; Petty, Michael C.

    2004-03-01

    The challenge of covalent linking a strong electron donor (as tetrathiafulvalene, TTF) to a strong acceptor (as tetracyanoquinodimethane, TCNQ) was laid down by Aviram and Ratner, who proposed that a single donor-sigma-acceptor molecule could rectify an electric current. Although numerous organic compounds have been tested in metal-molecule-metal junctions, they had substantially higher HOMO-LUMO gap (Eg >0.5 eV) and, in most cases, high dipole moment due to conjugated character of the linker. Those molecules re-orient in the electric field limiting the device stability. Recently, we have pioneered the synthesis of DsigmaA molecules with the HOMO-LUMO gap 0.17-0.3 eV, including the original TTF-TCNQ.* We will present the intriguing electronic properties of these compounds, including the conformational control of the Eg and the thermoexcited electron transfer. The compounds form high-quality LB films, suitable for molecular electronics applications. In Si-molecule-Ti junctions, the rectification ratio increases as molecules align perpendicularly to the surface, and the device stability override significantly the related system based on D-pi-A molecules. * Perepichka, et al., Angew. Chem. Int. Ed. 2003, 42, 4635.

  5. Ultrafast electron transfer in all-carbon-based SWCNT-C60 donor-acceptor nanoensembles connected by poly(phenylene-ethynylene) spacers

    NASA Astrophysics Data System (ADS)

    Barrejón, Myriam; Gobeze, Habtom B.; Gómez-Escalonilla, María J.; Fierro, José Luis G.; Zhang, Minfang; Yudasaka, Masako; Iijima, Sumio; D'Souza, Francis; Langa, Fernando

    2016-08-01

    Building all-carbon based functional materials for light energy harvesting applications could be a solution to tackle and reduce environmental carbon output. However, development of such all-carbon based donor-acceptor hybrids and demonstration of photoinduced charge separation in such nanohybrids is a challenge since in these hybrids part of the carbon material should act as an electron donating or accepting photosensitizer while the second part should fulfil the role of an electron acceptor or donor. In the present work, we have successfully addressed this issue by synthesizing covalently linked all-carbon-based donor-acceptor nanoensembles using single-walled carbon nanotubes (SWCNTs) as the donor and C60 as the acceptor. The donor-acceptor entities in the nanoensembles were connected by phenylene-ethynylene spacer units to achieve better electronic communication and to vary the distance between the components. These novel SWCNT-C60 nanoensembles have been characterized by a number of techniques, including TGA, FT-IR, Raman, AFM, absorbance and electrochemical methods. The moderate number of fullerene addends present on the side-walls of the nanotubes largely preserved the electronic structure of the nanotubes. The thermodynamic feasibility of charge separation in these nanoensembles was established using spectral and electrochemical data. Finally, occurrence of ultrafast electron transfer from the excited nanotubes in these donor-acceptor nanohybrids has been established by femtosecond transient absorption studies, signifying their utility in building light energy harvesting devices.Building all-carbon based functional materials for light energy harvesting applications could be a solution to tackle and reduce environmental carbon output. However, development of such all-carbon based donor-acceptor hybrids and demonstration of photoinduced charge separation in such nanohybrids is a challenge since in these hybrids part of the carbon material should act as an

  6. Spectral fine tuning of cyanine dyes: electron donor-acceptor substituted analogues of thiazole orange.

    PubMed

    Rastede, Elizabeth E; Tanha, Matteus; Yaron, David; Watkins, Simon C; Waggoner, Alan S; Armitage, Bruce A

    2015-09-26

    The introduction of electron donor and acceptor groups at strategic locations on a fluorogenic cyanine dye allows fine-tuning of the absorption and emission spectra while preserving the ability of the dye to bind to biomolecular hosts such as double-stranded DNA and a single-chain antibody fragment originally selected for binding to the parent unsubstituted dye, thiazole orange (TO). The observed spectral shifts are consistent with calculated HOMO-LUMO energy gaps and reflect electron density localization on the quinoline half of TO in the LUMO. A dye bearing donating methoxy and withdrawing trifluoromethyl groups on the benzothiazole and quinoline rings, respectively, shifts the absorption spectrum to sufficiently longer wavelengths to allow excitation at green wavelengths as opposed to the parent dye, which is optimally excited in the blue. PMID:26171668

  7. Spectral Fine Tuning of Cyanine Dyes: Electron Donor-Acceptor Substituted Analogues of Thiazole Orange†

    PubMed Central

    Rastede, Elizabeth E.; Tanha, Matteus; Yaron, David; Watkins, Simon C.; Waggoner, Alan S.; Armitage, Bruce A.

    2015-01-01

    The introduction of electron donor and acceptor groups at strategic locations on a fluorogenic cyanine dye allows fine-tuning of the absorption and emission spectra while preserving the ability of the dye to bind to biomolecular hosts such as double-stranded DNA and a single-chain antibody fragment originally selected for binding to the parent unsubstituted dye, thiazole orange (TO). The observed spectral shifts are consistent with calculated HOMO-LUMO energy gaps and reflect electron density localization on the quinoline half of TO in the LUMO. A dye bearing donating methoxy and withdrawing trifluoromethyl groups on the benzothiazole and quinoline rings, respectively, shifts the absorption spectrum to sufficiently longer wavelengths to allow excitation at green wavelengths as opposed to the parent dye, which is optimally excited in the blue. PMID:26171668

  8. Three component assemblies by orthogonal H-bonding and donor-acceptor charge-transfer interaction.

    PubMed

    Kar, Haridas; Ghosh, Suhrit

    2014-02-01

    Three component supramolecular assemblies from a mixture of an aromatic donor (D), acceptor (A) and external structure directing agent (ESDA) are achieved by orthogonal noncovalent interactions involving two different types of H-bonding and alternate D-A stacking. An ESDA containing amide or urea produces a charge-transfer gel and sol, respectively, owing to their contrasting morphology. PMID:24309620

  9. Electron Transfer within Self-Assembling Cyclic Tetramers Using Chlorophyll-Based Donor-Acceptor Building Blocks

    SciTech Connect

    Gunderson, Victoria L; Smeigh, Amanda L; Kim, Chul Hoon; Co, Dick T; Wasielewski, Michael R

    2012-05-09

    The synthesis and photoinduced charge transfer properties of a series of Chl-based donor-acceptor triad building blocks that self-assemble into cyclic tetramers are reported. Chlorophyll a was converted into zinc methyl 3-ethylpyrochlorophyllide a (Chl) and then further modified at its 20-position to covalently attach a pyromellitimide (PI) acceptor bearing a pyridine ligand and one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) secondary electron acceptors to give Chl-PI-NDI and Chl-PI-NDI2. The pyridine ligand within each ambident triad enables intermolecular Chl metal-ligand coordination in dry toluene, which results in the formation of cyclic tetramers in solution, as determined using small- and wide-angle X-ray scattering at a synchrotron source. Femtosecond and nanosecond transient absorption spectroscopy of the monomers in toluene-1% pyridine and the cyclic tetramers in toluene shows that the selective photoexcitation of Chl results in intramolecular electron transfer from 1*Chl to PI to form Chl+.-PI-.-NDI and Chl+.-PI-.-NDI2. This initial charge separation is followed by a rapid charge shift from PI-. to NDI and subsequent charge recombination of Chl+.-PI-NDI-. and Chl+.-PI-(NDI)NDI-. on a 5-30 ns time scale. Charge recombination in the Chl-PI-NDI2 cyclic tetramer (τCR = 30 ± 1 ns in toluene) is slower by a factor of 3 relative to the monomeric building blocks (τCR = 10 ± 1 ns in toluene-1% pyridine). This indicates that the self-assembly of these building blocks into the cyclic tetramers alters their structures in a way that lengthens their charge separation lifetimes, which is an advantageous strategy for artificial photosynthetic systems.

  10. Self-assembly properties of semiconducting donor-acceptor-donor bithienyl derivatives of tetrazine and thiadiazole-effect of the electron accepting central ring.

    PubMed

    Zapala, Joanna; Knor, Marek; Jaroch, Tomasz; Maranda-Niedbala, Agnieszka; Kurach, Ewa; Kotwica, Kamil; Nowakowski, Robert; Djurado, David; Pecaut, Jacques; Zagorska, Malgorzata; Pron, Adam

    2013-11-26

    Scanning tunneling microscopy was used to study the effect of the electron-accepting unit and the alkyl substituent's position on the type and extent of 2D supramolecular organization of penta-ring donor-acceptor-donor (DAD) semiconductors, consisting of either tetrazine or thiadiazole central acceptor ring symmetrically attached to two bithienyl groups. Microscopic observations of monomolecular layers on HOPG of four alkyl derivatives of the studied adsorbates indicate significant differences in their 2D organizations. Ordered monolayers of thiadiazole derivatives are relatively loose and, independent of the position of alkyl substituents, characterized by large intermolecular separation of acceptor units in the adjacent molecules located in the face-to-face configuration. The 2D supramolecular architecture in both derivatives of thiadiazole is very sensitive to the alkyl substituent's position. Significantly different behavior is observed for derivatives of tetrazine (which is a stronger electron acceptor). Stronger intermolecular DA interactions in these adsorbates generate an intermolecular shift in the monolayer, which is a dominant factor determining the 2D structural organization. As a consequence of this molecular arrangement, tetrazine groups (A segments) face thiophene rings (D segments) of the neighboring molecules. Monolayers of tetrazine derivatives are therefore much more densely packed and characterized by similar π-stacking of molecules independently of the position of alkyl substituents. Moreover, a comparative study of 3D supramolecular organization, deduced from the X-ray diffraction patterns, is also presented clearly confirming the polymorphism of the studied adsorbates. PMID:24228736

  11. Development of imide- and imidazole-containing electron acceptors for use in donor-acceptor conjugated compounds and polymers

    NASA Astrophysics Data System (ADS)

    Li, Duo

    Conjugated organic compounds and polymers have attracted significant attention due to their potential application in electronic devices as semiconducting materials, such as organic solar cells (OSCs). In order to tune band gaps, donor-acceptor (D-A) structure is widely used, which has been proved to be one of the most effective strategies. This thesis consists of three parts: 1) design, syntheses and characterization of new weak acceptors based on imides and the systematic study of the structure-property relationship; (2) introduction of weak and strong acceptors in one polymer to achieve a broad coverage of light absorption and improve the power conversion efficiency (PCE); (3) modification of benzothiadiazole (BT) acceptor in order to increase the electron withdrawing ability. Imide-based electron acceptors, 4-(5-bromothiophen-2-y1)-2-(2-ethylhexyl)-9- phenyl- 1H-benzo[f]isoindole-1,3(2H)-dione (BIDO-1) and 4,9-bis(5-bromothiophen-2-yl)-2-(2-ethylhexyl)-benzo[f]isoindole-1,3-dione (BIDO-2), were designed and synthesized. In this design, naphthalene is selected as its main core to maintain a planar structure, and thienyl groups are able to facilitate the bromination reaction and lower the band gap. BIDO-1 and BIDO-2 were successfully coupled with different donors by both Suzuki cross-coupling and Stille cross-coupling reactions. Based on the energy levels and band gaps of the BIDO-containing compounds and polymers, BIDO-1 and BIDO-2 are proved to be weak electron acceptors. Pyromellitic diimide (PMDI) was also studied and found to be a stronger electron acceptor than BIDO . In order to obtain broad absorption coverage, both weak acceptor ( BIDO-2) and strong acceptor diketopyrrolopyrrole (DPP) were introduced in the same polymer. The resulting polymers show two absorption bands at 400 and 600 nm and two emission peaks at 500 and 680 nm. The band gaps of the polymers are around 1.6 eV, which is ideal for OSC application. The PCE of 1.17% was achieved. Finally

  12. Synthesis and photophysical properties of new catenated electron donor-acceptor materials with magnesium and free base porphyrins as donors and C60 as the acceptor

    NASA Astrophysics Data System (ADS)

    Kirner, Sabrina V.; Guldi, Dirk M.; Megiatto, Jackson D., Jr.; Schuster, David I.

    2014-12-01

    A new series of nanoscale electron donor-acceptor systems with [2]catenane architectures has been synthesized, incorporating magnesium porphyrin (MgP) or free base porphyrin (H2P) as electron donor and C60 as electron acceptor, surrounding a central tetrahedral Cu(i)-1,10-phenanthroline (phen) complex. Model catenated compounds incorporating only one or none of these photoactive moieties were also prepared. The synthesis involved the use of Sauvage's metal template protocol in combination with the 1,3-dipolar cycloaddition of azides and alkynes (``click chemistry''), as in other recent reports from our laboratories. Ground state electron interactions between the individual constituents was probed using electrochemistry and UV-vis absorption spectroscopy, while events occurring following photoexcitation in tetrahydrofuran (under both aerobic and anaerobic conditions) at various wavelengths were followed by means of time-resolved transient absorption and emission spectroscopies on the femtosecond and nanosecond time scales, respectively, complemented by measurements of quantum yields for generation of singlet oxygen. From similar studies with model catenates containing one or neither of the chromophores, the events following photoexcitation could be elucidated. The results were compared with those previously reported for analogous catenates based on zinc porphyrin (ZnP). It was determined that a series of energy transfer (EnT) and electron transfer (ET) processes take place in the present catenates, ultimately generating long-distance charge separated (CS) states involving oxidized porphyrin and reduced C60 moieties, with lifetimes ranging from 400 to 1060 nanoseconds. Shorter lived short-distance CS states possessing oxidized copper complexes and reduced C60, with lifetimes ranging from 15 to 60 ns, were formed en route to the long-distance CS states. The dynamics of the ET processes were analyzed in terms of their thermodynamic driving forces. It was clear that

  13. Self-Assembly of Electron Donor-Acceptor-Based Carbazole Derivatives: Novel Fluorescent Organic Nanoprobes for Both One- and Two-Photon Cellular Imaging.

    PubMed

    Zhang, Jinfeng; Chen, Wencheng; Kalytchuk, Sergii; Li, King Fai; Chen, Rui; Adachi, Chihaya; Chen, Zhan; Rogach, Andrey L; Zhu, Guangyu; Yu, Peter K N; Zhang, Wenjun; Cheah, Kok Wai; Zhang, Xiaohong; Lee, Chun-Sing

    2016-05-11

    In this study, we report fluorescent organic nanoprobes with intense blue, green, and orange-red emissions prepared by self-assembling three carbazole derivatives into nanorods/nanoparticles. The three compounds consist of two or four electron-donating carbazole groups linked to a central dicyanobenzene electron acceptor. Steric hindrance from the carbazole groups leads to noncoplanar 3D molecular structures favorable to fluorescence in the solid state, while the donor-acceptor structures endow the molecules with good two-photon excited emission properties. The fluorescent organic nanoprobes exhibit good water dispersibility, low cytotoxicity, superior resistance against photodegradation and photobleaching. Both one- and two-photon fluorescent imaging were shown in the A549 cell line. Two-photon fluorescence imaging with the fluorescent probes was demonstrated to be more effective in visualizing and distinguishing cellular details compared to conventional one-photon fluorescence imaging. PMID:27097920

  14. Revealing the interactions between pentagon-octagon-pentagon defect graphene and organic donor/acceptor molecules: a theoretical study.

    PubMed

    Li, Jie-Wei; Liu, Yu-Yu; Xie, Ling-Hai; Shang, Jing-Zhi; Qian, Yan; Yi, Ming-Dong; Yu, Ting; Huang, Wei

    2015-02-21

    Defect engineering and the non-covalent interaction strategy allow for dramatically tuning the optoelectronic features of graphene. Herein, we theoretically investigated the intrinsic mechanism of non-covalent interactions between pentagon-octagon-pentagon (5-8-5) defect graphene (DG) and absorbed molecules, tetrathiafulvalene (TTF), perfluoronaphthalene (FNa), tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), through geometry, distance, interaction energy, Mulliken charge distribution, terahertz frequency vibration, visualization of the interactions, charge density difference, electronic transition behaviour, band structure and density of state. All the calculations were performed using density functional theory including a dispersion correction (DFT-D). The calculated results indicate that the cyano- (CN) group (electron withdraw group) in TCNQ and F4TCNQ, rather than the F group, gain the electron from DG effectively and exhibit much stronger interactions via wavefunction overlap with DG, leading to a short non-covalent interaction distance, a large interaction energy and a red-shift of out-of-plane terahertz frequency vibration, changing the bands near the Fermi level and enhancing the infrared (IR) light absorption significantly. The enhancement of such IR absorbance offering a broader absorption (from 300 to 1200 nm) will benefit light harvesting in potential applications of solar energy conversion. PMID:25559269

  15. Density functional study of the electronic structure of dye-functionalized fullerenes and their model donor-acceptor complexes containing P3HT.

    PubMed

    Baruah, Tunna; Garnica, Amanda; Paggen, Marina; Basurto, Luis; Zope, Rajendra R

    2016-04-14

    We study the electronic structure of C60 fullerenes functionalized with a thiophene-diketo-pyrrolopyrrole-thiophene based chromophore using density functional theory combined with large polarized basis sets. As the attached chromophore has electron donor character, the functionalization of the fullerene leads to a donor-acceptor (DA) system. We examine in detail the effect of the linker and the addition site on the electronic structure of the functionalized fullerenes. We further study the electronic structure of these DA complexes with a focus on the charge transfer excitations. Finally, we examine the interface of the functionalized fullerenes with the widely used poly(3-hexylthiophene-2,5-diyl) (P3HT) donor. Our results show that all functionalized fullerenes with an exception of the C60-pyrrolidine [6,6], where the pyrrolidine is attached at a [6,6] site, have larger electron affinities relative to the pristine C60 fullerene. We also estimate the quasi-particle gap, lowest charge transfer excitation energy, and the exciton binding energies of the functionalized fullerene-P3MT model systems. Results show that the exciton binding energies in these model complexes are slightly smaller compared to a similarly prepared phenyl-C61-butyric acid methyl ester (PCBM)-P3MT complex. PMID:27083718

  16. Density functional study of the electronic structure of dye-functionalized fullerenes and their model donor-acceptor complexes containing P3HT

    NASA Astrophysics Data System (ADS)

    Baruah, Tunna; Garnica, Amanda; Paggen, Marina; Basurto, Luis; Zope, Rajendra R.

    2016-04-01

    We study the electronic structure of C60 fullerenes functionalized with a thiophene-diketo-pyrrolopyrrole-thiophene based chromophore using density functional theory combined with large polarized basis sets. As the attached chromophore has electron donor character, the functionalization of the fullerene leads to a donor-acceptor (DA) system. We examine in detail the effect of the linker and the addition site on the electronic structure of the functionalized fullerenes. We further study the electronic structure of these DA complexes with a focus on the charge transfer excitations. Finally, we examine the interface of the functionalized fullerenes with the widely used poly(3-hexylthiophene-2,5-diyl) (P3HT) donor. Our results show that all functionalized fullerenes with an exception of the C60-pyrrolidine [6,6], where the pyrrolidine is attached at a [6,6] site, have larger electron affinities relative to the pristine C60 fullerene. We also estimate the quasi-particle gap, lowest charge transfer excitation energy, and the exciton binding energies of the functionalized fullerene-P3MT model systems. Results show that the exciton binding energies in these model complexes are slightly smaller compared to a similarly prepared phenyl-C61-butyric acid methyl ester (PCBM)-P3MT complex.

  17. Tuning Optical and Electron Donor Properties by Peripheral Thio-Aryl Substitution of Subphthalocyanine: A New Series of Donor-Acceptor Hybrids for Photoinduced Charge Separation.

    PubMed

    Kc, Chandra B; Lim, Gary N; D'Souza, Francis

    2016-09-01

    Subphthalocyanine (SubPc), a unique ring-reduced member of the common phthalocyanines family, although known for its higher absorptivity, reveals narrow absorption with peak maxima around 570 nm thus limiting its utility in light-energy-harvesting applications. In the present study, by peripheral thio-aryl substitution of SubPc macrocycle, the spectral properties have been modulated to extend the absorption and emission well into the visible/near-IR region. Additionally, for α-ring-substituted derivatives, facile oxidation of SubPc was witnessed, thus making these derivatives better electron donors. Next, the preparation of donor-acceptor dyads containing the well-known electron acceptor C60 connected to the central boron atom of SubPc was accomplished by making use of the 1,3-dipolar cycloaddition reaction. Control experiments and free-energy calculations using the redox and spectral data suggested that the observed fluorescence quenching of SubPc in these dyads is due to electron transfer. Accordingly, transient spectral studies performed both in polar and nonpolar solvents conclusively proved electron transfer to be the quenching mechanism in these dyads. The measured rate constants by fitting kinetic data revealed efficient charge separation and charge recombination processes, suggesting that these dyads could be useful materials for the construction of light-to-electricity or light-to-fuel production devices. PMID:27515576

  18. Easy Access to NO2 -Containing Donor-Acceptor-Acceptor Electron Donors for High Efficiency Small-Molecule Organic Solar Cells.

    PubMed

    Ting, Hao-Chun; Yang, Ya-Ting; Chen, Chia-Hsun; Lee, Jiun-Haw; Chang, Jung-Hung; Wu, Chih-I; Chiu, Tien-Lung; Lin, Chi-Feng; Chung, Chin-Lung; Wong, Ken-Tsung

    2016-06-22

    Two donor-acceptor-acceptor (D-A-A)-type molecules incorporating nitrobenzoxadiazole (NBO) as the A-A block and ditolylamine as the D block bridged through a phenylene (PNBO) and a thiophene (TNBO) spacer were synthesized in a one-step coupling reaction. Their electronic, photophysical, and thermal properties; crystallographic analysis; and theoretical calculations were studied to establish a clear structure-property relationship. The results indicate that the quinoidal character of the thiophene bridge strongly governs the structural features and crystal packings (herringbone vs. brickwork) and thus the physical properties of the compounds. PNBO and TNBO were utilized as electron donors combined with C70 as the electron acceptor in the active layer of vacuum-processed bulk heterojunction small-molecule organic solar cells (SMOSCs). The power conversion efficiency of both PNBO- and TNBO-based OSCs exceeded 5 %. The ease of accessibility of PNBO and TNBO demonstrates the potential for simple and economical synthesis of electron donors in vacuum-processed SMOSCs. PMID:27213296

  19. Photobehavior of the geometrical isomers of two 1,4-distyrylbenzene analogues with side groups of different electron donor/acceptor character.

    PubMed

    Ciorba, S; Galiazzo, G; Mazzucato, U; Spalletti, A

    2010-10-14

    The photobehavior of two 1,4-distyrylbenzene analogues where the central benzene ring is asymmetrically substituted with a pyrid-4-ylethenyl group at one side and thien-2-ylethenyl or a p-nitrostyryl group at the other side, has been studied in two solvents at room temperature. The four geometrical isomers (EE, ZE, EZ, and ZZ) of each compound were separated by the combined use of HPLC and spectrophotometric techniques. The radiative/reactive competition in their excited state relaxation was particularly examined: the diabatic/adiabatic contributions were estimated and a reasonable interpretation of the photoisomerization mechanism was proposed. The role of the conformational isomers was also investigated by measured and computed spectral data. Since the different electron donor/acceptor character of the side groups of these molecules can induce charge transfer phenomena that can affect the relaxation pathways of their excited states, the photobehavior was compared in inert and polar solvents to clarify the role of the intramolecular charge transfer. The latter was found to affect markedly the relaxation properties and to induce interesting fluorosolvatochromic effects, particularly in the p-nitro derivative. The participation of the triplet state in the reaction mechanism of the latter was also investigated by flash photolysis and sensitized experiments. PMID:20857985

  20. Electronic and optical properties of novel carbazole-based donor-acceptor compounds for applications in blue-emitting organic light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Legaspi, Christian M.; Stubbs, Regan E.; Yaron, David J.; Peteanu, Linda A.; Sfeir, Matthew Y.; Kemboi, Abraham; Picker, Jesse; Fossum, Eric

    2015-08-01

    Organic light-emitting diodes (OLEDs) have received a significant attention over the past decade due to their energy-saving potential. We have recently synthesized two novel carbazole-based donor-acceptor compounds and analyzed their optical properties to determine their suitability for use as blue emitters in OLEDs. These compounds show remarkable photo-stability and high quantum yields in the blue region of the spectrum. In addition, they have highly solvatochromic emission. In non-polar solvents, bright, blue-shifted (λmax ≈ 398 nm), and highly structured emission is seen. With increasing solvent dielectric constant, the emission becomes weaker, red-shifted (λmax ≈ 507 nm), and broad. We aim to determine the underlying cause of these changes. Electronic structure calculations indicate the presence of multiple excited states with comparable oscillator strength. These states are of interest because there are several with charge-transfer (CT) character, and others centered on the donor moiety. We theorize that CT states play a role in the observed changes in emission lineshape and may promote charge mobility for electrofluorescence in OLEDs. In the future, we plan to use Stark spectroscopy to analyze the polarity of excited states and transient absorption spectroscopy to observe the dynamics in the excited state.

  1. Bimolecular electron transfer reactions in coumarin amine systems: Donor acceptor orientational effect on diffusion-controlled reaction rates

    NASA Astrophysics Data System (ADS)

    Satpati, A. K.; Nath, S.; Kumbhakar, M.; Maity, D. K.; Senthilkumar, S.; Pal, H.

    2008-04-01

    Electron transfer (ET) reactions between excited coumarin dyes and different aliphatic amine (AlA) and aromatic amine (ArA) donors have been investigated in acetonitrile solution using steady-state (SS) and time-resolved (TR) fluorescence quenching measurements. No ground state complex or emissive exciplex formation has been indicated in these systems. SS and TR measurements give similar quenching constants ( kq) for each of the coumarin-amine pairs, suggesting dynamic nature of interaction in these systems. On correlating kq values with the free energy changes (Δ G0) of the ET reactions show the typical Rehm-Weller type of behavior as expected for bimolecular ET reactions under diffusive condition, where kq increases with -Δ G0 at the lower exergonicity (-Δ G0) region but ultimately saturate to a diffusion-limited value (kqDC) at the higher exergonicity region. It is, however, interestingly observed that the kqDC values vary largely depending on the type of the amines used. Thus, kqDC is much higher with ArAs than AlAs. Similarly, the kqDC for cyclic monoamine 1-azabicyclo-[2,2,2]-octane (ABCO) is distinctly lower and that for cyclic diamine 1,4-diazabicyclo-[2,2,2]-octane (DABCO) is distinctly higher than the kqDC value obtained for other noncyclic AlAs. These differences in the kqDC values have been rationalized on the basis of the differences in the orientational restrictions involved in the ET reactions with different types of amines. As understood, n-type donors (AlAs) introduce large orientational restriction and thus significantly reduces the ET efficiency in comparison to the π-type donors (ArAs). Structural constrains are inferred to be the reason for the differences in the kqDC values involving ABCO, DABCO donors in comparison to other noncyclic AlAs. Supportive evidence for the orientational restrictions involving different types of amines donors has also been obtained from DFT based quantum chemical calculations on the molecular orbitals of

  2. Efficient Synthesis and Photosensitizer Performance of Nonplanar Organic Donor-Acceptor Molecules.

    PubMed

    Yuan, Yuping; Michinobu, Tsuyoshi; Satoh, Norifusa; Ashizawa, Minoru; Han, Liyuan

    2015-08-01

    Nonplanar organic donor-acceptor molecules bearing a carboxylic acid group were synthesized by the formal [2+2] cycloaddition-retroelectrocyclization reaction between aniline-substituted alkynes and tetracyanoethylene (TCNE) or 7,7,8,8-tetracyanoquinodimethane (TCNQ). This reaction offers an atom-economic one-step approach to donor-acceptor chromophores in satisfactory high yields. The resulting donor-acceptor molecules were characterized by conventional analytical techniques. In addition, the nonplanarity and intermolecular interactions were investigated by X-ray crystallography. The energy levels and intramolecular charge-transfer (CT), evaluated by UV-Vis-near IR spectroscopy and electrochemistry, suggested that there is a linear correlation between the optical and electrochemical band gaps. Based on these structural and electronic analyses, the photosensitizer performances of the donor-acceptor molecules in dye-sensitized solar cells (DSSCs) were initially investigated using TiO2 or SnO2 electrodes. Although the power conversion efficiencies were limited, the incident-photon-to-current-conversion efficiency (IPCE) spectra indicated a better photocurrent generation for the devices on SnO2 as compared to those on TiO2. PMID:26369162

  3. Long-range coupling of electron-hole pairs in spatially separated organic donor-acceptor layers

    PubMed Central

    Nakanotani, Hajime; Furukawa, Taro; Morimoto, Kei; Adachi, Chihaya

    2016-01-01

    Understanding exciton behavior in organic semiconductor molecules is crucial for the development of organic semiconductor-based excitonic devices such as organic light-emitting diodes and organic solar cells, and the tightly bound electron-hole pair forming an exciton is normally assumed to be localized on an organic semiconducting molecule. We report the observation of long-range coupling of electron-hole pairs in spatially separated electron-donating and electron-accepting molecules across a 10-nanometers-thick spacer layer. We found that the exciton energy can be tuned over 100 megaelectron volts and the fraction of delayed fluorescence can be increased by adjusting the spacer-layer thickness. Furthermore, increasing the spacer-layer thickness produced an organic light-emitting diode with an electroluminescence efficiency nearly eight times higher than that of a device without a spacer layer. Our results demonstrate the first example of a long-range coupled charge-transfer state between electron-donating and electron-accepting molecules in a working device. PMID:26933691

  4. Ultrafast Photoinduced Electron Transfer and Charge Stabilization in Donor-Acceptor Dyads Capable of Harvesting Near-Infrared Light.

    PubMed

    Bandi, Venugopal; Gobeze, Habtom B; D'Souza, Francis

    2015-08-01

    To harvest energy from the near-infrared (near-IR) and infrared (IR) regions of the electromagnetic spectrum, which constitutes nearly 70 % of the solar radiation, there is a great demand for near-IR and IR light-absorbing sensitizers that are capable of undergoing ultrafast photoinduced electron transfer when connected to a suitable electron acceptor. Towards achieving this goal, in the present study, we report multistep syntheses of dyads derived from structurally modified BF2-chelated azadipyrromethene (ADP; to extend absorption and emission into the near-IR region) and fullerene as electron-donor and electron-acceptor entities, respectively. The newly synthesized dyads were fully characterized based on optical absorbance, fluorescence, geometry optimization, and electrochemical studies. The established energy level diagram revealed the possibility of electron transfer either from the singlet excited near-IR sensitizer or singlet excited fullerene. Femtosecond and nanosecond transient absorption studies were performed to gather evidence of excited state electron transfer and to evaluate the kinetics of charge separation and charge recombination processes. These studies revealed the occurrence of ultrafast photoinduced electron transfer leading to charge stabilization in the dyads, and populating the triplet states of ADP, benzanulated-ADP and benzanulated thiophene-ADP in the respective dyads, and triplet state of C60 in the case of BF2 -chelated dipyrromethene derived dyad during charge recombination. The present findings reveal that these sensitizers are suitable for harvesting light energy from the near-IR region of the solar spectrum and for building fast-responding optoelectronic devices operating under near-IR radiation input. PMID:26130432

  5. A photon-working on/off switch for intramolecular donor-acceptor interactions and invisible modulation of the fluorescence.

    PubMed

    Takeuchi, Sakiko; Nakagawa, Tetsuya; Yokoyama, Yasushi

    2016-03-01

    An on/off switching for charge-transfer interactions between the side chains of a diarylethene based on photochromic reactions has been proved by the disappearance and appearance of an additional fluorescence band. PMID:26906945

  6. Electronic structure, molecular orientation, charge transfer dynamics and solar cells performance in donor/acceptor copolymers and fullerene: Experimental and theoretical approaches

    SciTech Connect

    Garcia-Basabe, Y.; Borges, B. G. A. L.; Rocco, M. L. M. E-mail: luiza@iq.ufrj.br; Marchiori, C. F. N.; Yamamoto, N. A. D.; Koehler, M.; Roman, L. S. E-mail: luiza@iq.ufrj.br; Macedo, A. G.

    2014-04-07

    By combining experimental and theoretical approaches, the electronic structure, molecular orientation, charge transfer dynamics and solar cell performance in donor/acceptor copolymer poly[2,7-(9,9-bis(2-ethylhexyl)-dibenzosilole)-alt-4,7-bis(thiophen-2-yl) benzo-2,1,3-thiadiazole] (PSiF-DBT) films and blended with 6,6.-phenyl-C 61-butyric acid methyl ester (PSiF-DBT:PCBM) were investigated. Good agreement between experimental and theoretical PSiF-DBT UV-Vis absorption spectrum is observed and the main molecular orbitals contributing to the spectrum were determined using DFT single point calculations. Non-coplanar configuration was determined by geometric optimization calculation in isolated PSiF-DBT pentamer and corroborated by angular variation of the sulphur 1s near-edge X-ray absorption fine structure (NEXAFS) spectra. Edge-on and plane-on molecular orientations were obtained for thiophene and benzothiadiazole units, respectively. A power conversion efficiency up to 1.58%, open circuit voltage of 0.51 V, short circuit current of 8.71 mA/cm{sup 2} and a fill factor of 35% was obtained using blended PSiF-DBT:PCBM as active layer in a bulk heterojunction solar cell. Ultrafast electron dynamics in the low-femtosecond regime was evaluated by resonant Auger spectroscopy using the core-hole clock methodology around sulphur 1s absorption edge. Electron delocalization times for PSiF-DBT and PSiF-DBT:PCBM polymeric films were derived for selected excitation energies corresponding to the main transitions in the sulphur 1s NEXAFS spectra. The mixture of PSiF-DBT with PCBM improves the charge transfer process involving the π* molecular orbital of the thiophene units.

  7. Magnetic field enhanced electroluminescence in organic light emitting diodes based on electron donor-acceptor exciplex blends

    NASA Astrophysics Data System (ADS)

    Baniya, Sangita; Basel, Tek; Sun, Dali; McLaughlin, Ryan; Vardeny, Zeev Valy

    2016-03-01

    A useful process for light harvesting from injected electron-hole pairs in organic light emitting diodes (OLED) is the transfer from triplet excitons (T) to singlet excitons (S) via reverse intersystem crossing (RISC). This process adds a delayed electro-luminescence (EL) emission component that is known as thermally activated delayed fluorescence (TADF). We have studied electron donor (D)/acceptor(A) blends that form an exciplex manifold in which the energy difference, ΔEST between the lowest singlet (S1) and triplet (T1) levels is relatively small (<100 meV), and thus allows RISC at ambient temperature. We found that the EL emission in OLED based on the exciplex blend is enhanced up to 40% by applying a relatively weak magnetic field of 50 mT at ambient. Moreover the MEL response is activated with activation energy similar that of the EL emission. This suggests that the large magneto-EL originates from an additional spin-mixing channel between singlet and triplet states of the generated exciplexes, which is due to TADF. We will report on the MEL dependencies on the temperature, bias voltage, and D-A materials for optimum OLED performance. Supported by SAMSUNG Global Research Outreach (GRO) program, and also by the NSF-Material Science & Engineering Center (MRSEC) program at the University of Utah (DMR-1121252).

  8. An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

    NASA Astrophysics Data System (ADS)

    Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

    2015-07-01

    In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting.

  9. An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

    PubMed Central

    Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

    2015-01-01

    In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting. PMID:26174201

  10. Deep proton tunneling in the electronically adiabatic and non-adiabatic limits: Comparison of the quantum and classical treatment of donor-acceptor motion in a protein environment

    NASA Astrophysics Data System (ADS)

    Benabbas, Abdelkrim; Salna, Bridget; Sage, J. Timothy; Champion, Paul M.

    2015-03-01

    Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical "gating" distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working near

  11. Deep proton tunneling in the electronically adiabatic and non-adiabatic limits: Comparison of the quantum and classical treatment of donor-acceptor motion in a protein environment

    SciTech Connect

    Benabbas, Abdelkrim; Salna, Bridget; Sage, J. Timothy; Champion, Paul M.

    2015-03-21

    Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical “gating” distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working

  12. Deep proton tunneling in the electronically adiabatic and non-adiabatic limits: comparison of the quantum and classical treatment of donor-acceptor motion in a protein environment.

    PubMed

    Benabbas, Abdelkrim; Salna, Bridget; Sage, J Timothy; Champion, Paul M

    2015-03-21

    Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical "gating" distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working near

  13. Bright Solid-State Emission of Disilane-Bridged Donor-Acceptor-Donor and Acceptor-Donor-Acceptor Chromophores.

    PubMed

    Shimada, Masaki; Tsuchiya, Mizuho; Sakamoto, Ryota; Yamanoi, Yoshinori; Nishibori, Eiji; Sugimoto, Kunihisa; Nishihara, Hiroshi

    2016-02-01

    The development of disilane-bridged donor-acceptor-donor (D-Si-Si-A-Si-Si-D) and acceptor-donor-acceptor (A-Si-Si-D-Si-Si-A) compounds is described. Both types of compound showed strong emission (λem =ca. 500 and ca. 400 nm, respectively) in the solid state with high quantum yields (Φ: up to 0.85). Compound 4 exhibited aggregation-induced emission enhancement in solution. X-ray diffraction revealed that the crystal structures of 2, 4, and 12 had no intermolecular π-π interactions to suppress the nonradiative transition in the solid state. PMID:26822564

  14. Electronic energy and electron transfer processes in photoexcited donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units.

    PubMed

    Lee, K J; Woo, J H; Kim, E; Xiao, Y; Su, X; Mazur, L M; Attias, A-J; Fages, F; Cregut, O; Barsella, A; Mathevet, F; Mager, L; Wu, J W; D'Aléo, A; Ribierre, J-C

    2016-03-01

    We investigate the photophysical properties of organic donor-acceptor dyad and triad molecular systems based on triphenylene and perylene diimide units linked by a non-conjugated flexible bridge in solution using complementary optical spectroscopy techniques. When these molecules are diluted in dichloromethane solution, energy transfer from the triphenylene to the perylene diimide excited moieties is evidenced by time-resolved fluorescence measurements resulting in a quenching of the emission from the triphenylene moieties. Simultaneously, another quenching process that affects the emission from both donor and acceptor units is observed. Solution ultrafast transient absorption measurements provide evidence of photo-induced charge transfer from either the donor or the acceptor depending upon the excitation. Overall, the analysis of the detailed time-resolved spectroscopic measurements carried out in the dyad and triad systems as well as in the triphenylene and perylene diimide units alone provides useful information both to better understand the relations between energy and charge transfer processes with molecular structures, and for the design of future functional dyad and triad architectures based on donor and acceptor moieties for organic optoelectronic applications. PMID:26911420

  15. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers

    NASA Astrophysics Data System (ADS)

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N. V.; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-12-01

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affinities of the donor and the acceptor, the triplet-triplet state can have a stronger oscillator strength than the charge-transfer exciton. We discuss the possibility of intramolecular singlet fission from the triplet-triplet state, and how such fission can be detected experimentally.

  16. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers.

    PubMed

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N V; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-12-31

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affinities of the donor and the acceptor, the triplet-triplet state can have a stronger oscillator strength than the charge-transfer exciton. We discuss the possibility of intramolecular singlet fission from the triplet-triplet state, and how such fission can be detected experimentally. PMID:26765027

  17. Photoelectric covalent organic frameworks: converting open lattices into ordered donor-acceptor heterojunctions.

    PubMed

    Chen, Long; Furukawa, Ko; Gao, Jia; Nagai, Atsushi; Nakamura, Toshikazu; Dong, Yuping; Jiang, Donglin

    2014-07-16

    Ordered one-dimensional open channels represent the typical porous structure of two-dimensional covalent organic frameworks (COFs). Here we report a general synthetic strategy for converting these open lattice structures into ordered donor-acceptor heterojunctions. A three-component topological design scheme was explored to prepare electron-donating intermediate COFs, which upon click reaction were transformed to photoelectric COFs with segregated donor-acceptor alignments, whereas electron-accepting buckyballs were spatially confined within the nanochannels via covalent anchoring on the channel walls. The donor-acceptor heterojunctions trigger photoinduced electron transfer and allow charge separation with radical species delocalized in the π-arrays, whereas the charge separation efficiency was dependent on the buckyball content. This new donor-acceptor strategy explores both skeletons and pores of COFs for charge separation and photoenergy conversion. PMID:24963896

  18. Evaluating the Performance of DFT Functionals in Assessing the Interaction Energy and Ground-State Charge Transfer of Donor/Acceptor Complexes: Tetrathiafulvalene-Tetracyanoquinodimethane (TTF-TCNQ) as a Model Case.

    PubMed

    Sini, Gjergji; Sears, John S; Brédas, Jean-Luc

    2011-03-01

    We have evaluated the performance of several density functional theory (DFT) functionals for the description of the ground-state electronic structure and charge transfer in donor/acceptor complexes. The tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) complex has been considered as a model test case. Hybrid functionals have been chosen together with recently proposed long-range corrected functionals (ωB97X, ωB97X-D, LRC-ωPBEh, and LC-ωPBE) in order to assess the sensitivity of the results to the treatment and magnitude of exact exchange. The results show an approximately linear dependence of the ground-state charge transfer with the HOMOTTF-LUMOTCNQ energy gap, which in turn depends linearly on the percentage of exact exchange in the functional. The reliability of ground-state charge transfer values calculated in the framework of a monodeterminantal DFT approach was also examined. PMID:26596294

  19. Optically tunable spin-exchange energy at donor:acceptor interfaces in organic solar cells

    SciTech Connect

    Li, Mingxing; Wang, Hongfeng; He, Lei; Zang, Huidong; Xu, Hengxing; Hu, Bin

    2014-07-14

    Spin-exchange energy is a critical parameter in controlling spin-dependent optic, electronic, and magnetic properties in organic materials. This article reports optically tunable spin-exchange energy by studying the line-shape characteristics in magnetic field effect of photocurrent developed from intermolecular charge-transfer states based on donor:acceptor (P3HT:PCBM) system. Specifically, we divide magnetic field effect of photocurrent into hyperfine (at low field < 10 mT) and spin-exchange (at high field > 10 mT) regimes. We observe that increasing photoexcitation intensity can lead to a significant line-shape narrowing in magnetic field effect of photocurrent occurring at the spin-exchange regime. We analyze that the line-shape characteristics is essentially determined by the changing rate of magnetic field-dependent singlet/triplet ratio when a magnetic field perturbs the singlet-triplet transition through spin mixing. Based on our analysis, the line-shape narrowing results indicate that the spin-exchange energy at D:A interfaces can be optically changed by changing photoexcitation intensity through the interactions between intermolecular charge-transfer states. Therefore, our experimental results demonstrate an optical approach to change the spin-exchange energy through the interactions between intermolecular charge-transfer states at donor:acceptor interface in organic materials.

  20. Design directed self-assembly of donor-acceptor polymers.

    PubMed

    Marszalek, Tomasz; Li, Mengmeng; Pisula, Wojciech

    2016-09-21

    Donor-acceptor polymers with an alternating array of donor and acceptor moieties have gained particular attention during recent years as active components of organic electronics. By implementation of suitable subunits within the conjugated backbone, these polymers can be made either electron-deficient or -rich. Additionally, their band gap and light absorption can be precisely tuned for improved light-harvesting in solar cells. On the other hand, the polymer design can also be modified to encode the desired supramolecular self-assembly in the solid-state that is essential for an unhindered transport of charge carriers. This review focuses on three major factors playing a role in the assembly of donor-acceptor polymers on surfaces which are (1) nature, geometry and substitution position of solubilizing alkyl side chains, (2) shape of the conjugated polymer defined by the backbone curvature, and (3) molecular weight which determines the conjugation length of the polymer. These factors adjust the fine balance between attractive and repulsive forces and ensure a close polymer packing important for an efficient charge hopping between neighboring chains. On the microscopic scale, an appropriate domain formation with a low density of structural defects in the solution deposited thin film is crucial for the charge transport. The charge carrier transport through such thin films is characterized by field-effect transistors as basic electronic elements. PMID:27440174

  1. Synthesis of dithienosilole-based highly photoluminescent donor-acceptor type compounds.

    PubMed

    Ohshita, Joji; Tominaga, Yuta; Tanaka, Daiki; Ooyama, Yousuke; Mizumo, Tomonobu; Kobayashi, Norifumi; Higashimura, Hideyuki

    2013-03-14

    Highly photoluminescent acceptor-donor-acceptor (A-D-A) and donor-acceptor (D-A) type compounds with a dithienosilole unit as the donor and perfluorotolyl or dimesitylboryl group(s) as the acceptor were prepared by the reaction of lithiated dithienosilole derivatives with perfluorotoluene or fluorodimesitylborane, respectively. The resulting A-D-A and D-A type compounds showed red-shifted UV absorption and PL bands compared to those of simple dithienosiloles having no acceptor units, reported previously, and were highly photoluminescent in the solid state as well as in solution. Solvatochromic behaviour that would arise from the intramolecular donor-acceptor interaction were observed for the D-A type compounds with respect to the UV absorption and PL spectra. In addition, it was found that bis(dimesitylboryl)dithienosilole and (dimesitylboryl)(methylthio)dithienosilole responded to coexisting fluoride anions, leading to clear UV absorption and PL spectral changes in solutions. PMID:23295388

  2. Electronic structure of p-type perylene monoimide-based donor-acceptor dyes on the nickel oxide (100) surface: a DFT approach.

    PubMed

    Kontkanen, O V; Niskanen, M; Hukka, T I; Rantala, T T

    2016-05-25

    A p-type dye-sensitized solar cell, where the dye injects a hole into the semiconductor, could be combined with a typical Grätzel cell to create an efficient tandem device. However, the current p-type devices suffer from low efficiency. Here, geometries and electronic structures of four perylenemonoimide-based dyes () both as free and adsorbed on the NiO(100) semiconductor surface have been investigated to gain a better understanding of the p-type devices. In particular, the electronic transitions relevant to charge transfer between the dye and the surface have been identified. Excitations have been evaluated using the time-dependent DFT calculations, and the roles of frontier orbitals and band edges in transitions have been assessed. The adsorbed dyes can adopt either upright or slightly tilted geometries depending on the structure of the anchoring group and the binding mode of the dye. The adsorption slightly lowers the NiO band gap, from 4.06 eV to 3.90-3.96 eV, depending on the surface-adsorbate system and the band gaps of the dye molecules by 0.1-0.2 eV. Additionally, the adsorption mode of dye moves the LUMO+1 level down by 0.5 eV. The effective mass of charge carrier holes is significantly smaller at the NiO surface than in the bulk indicating the importance of surface conductivity. We also found that the potential drop, i.e. the driving force for charge transfer from NiO to the dye molecule, depends on the adsorption mode of . PMID:27224900

  3. Donor-acceptor conjugated polymers based on multifused ladder-type arenes for organic solar cells.

    PubMed

    Wu, Jhong-Sian; Cheng, Sheng-Wen; Cheng, Yen-Ju; Hsu, Chain-Shu

    2015-03-01

    Harvesting solar energy from sunlight to generate electricity is considered as one of the most important technologies to address the future sustainability of humans. Polymer solar cells (PSCs) have attracted tremendous interest and attention over the past two decades due to their potential advantage to be fabricated onto large area and light-weight flexible substrates by solution processing at a lower cost. PSCs based on the concept of bulk heterojunction (BHJ) configuration where an active layer comprises a composite of a p-type (donor) and an n-type (acceptor) material represents the most useful strategy to maximize the internal donor-acceptor interfacial area allowing for efficient charge separation. Fullerene derivatives such as [6,6]-phenyl-C61 or 71-butyric acid methyl ester (PCBM) are the ideal n-type materials ubiquitously used for BHJ solar cells. The major effort to develop photoactive materials is numerously focused on the p-type conjugated polymers which are generally synthesized by polymerization of electron-rich donor and electron-deficient acceptor monomers. Compared to the development of electron-deficient comonomers (acceptor segments), the development of electron-rich donor materials is considerably flourishing. Forced planarization by covalently fastening adjacent aromatic and heteroaromatic subunits leads to the formation of ladder-type conjugated structures which are capable of elongating effective conjugation, reducing the optical bandgap, promoting intermolecular π-π interactions and enhancing intrinsic charge mobility. In this review, we will summarize the recent progress on the development of various well-defined new ladder-type conjugated materials. These materials serve as the superb donor monomers to prepare a range of donor-acceptor semi-ladder copolymers with sufficient solution-processability for solar cell applications. PMID:25322211

  4. Organic Materials in the Undergraduate Laboratory: Microscale Synthesis and Investigation of a Donor-Acceptor Molecule

    ERIC Educational Resources Information Center

    Pappenfus, Ted M.; Schliep, Karl B.; Dissanayake, Anudaththa; Ludden, Trevor; Nieto-Ortega, Belen; Lopez Navarrete, Juan T.; Ruiz Delgado, M. Carmen; Casado, Juan

    2012-01-01

    A series of experiments for undergraduate courses (e.g., organic, physical) have been developed in the area of small molecule organic materials. These experiments focus on understanding the electronic and redox properties of a donor-acceptor molecule that is prepared in a convenient one-step microscale reaction. The resulting intensely colored…

  5. An extended Foerster-Dexter model for correlated donor-acceptor placement in solid state materials

    NASA Astrophysics Data System (ADS)

    Rotman, S. R.; Hartmann, F. X.

    1987-09-01

    The current theory of donor-acceptor interactions in solid-state materials is based on a random distribution of donors and acceptors through the crystal. In this paper, we present a model to calculate the observable transfer rates for the correlated positioning of donors and acceptors in laser materials. Chemical effects leading to such correlations are discussed.

  6. Synthesis and characterization of a highly strained donor-acceptor nanohoop.

    PubMed

    Van Raden, J M; Darzi, E R; Zakharov, L N; Jasti, R

    2016-06-15

    A highly-strained, nitrogen-doped cycloparaphenylene (CPP), aza[6]CPP, was synthesized and then converted to a donor-acceptor nanohoop, N-methylaza[6]CPP, via alkylation of the nitrogen center. The energy levels of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) for both molecules were then probed by cyclic voltammetry (CV), which revealed that the donor-acceptor nanohoop had a significantly lower LUMO energy relative to [6]CPP and aza[6]CPP. Density functional theory (DFT) revealed that the donor-acceptor nanohoop underwent a redistribution of the frontier molecular orbital (FMO) density such that a significant portion of the LUMO density resided upon the electron-deficient nitrogen-containing ring. This localization of LUMO density caused a large lowering in the LUMO energy of nearly a full electron volt, while the HOMO energy was less affected due to a large centralization of the FMO on the electron-rich phenylene backbone. This ultimately resulted in a net lowering of the HOMO-LUMO energy gap which was observed both experimentally and computationally. In addition, N-methylaza[6]CPP has a significantly lower energy LUMO than N-methylaza[8]CPP, illustrating that the FMO levels of donor-acceptor nanohoops can be tuned by adjusting the hoop size. PMID:26881906

  7. Red-shifted cyanide stretching frequencies in cyanide-bridged transition metal donor-acceptor complexes. Support for vibronic coupling

    SciTech Connect

    Watzky, M.A.; Endicott, J.F.; Song, X.

    1996-06-05

    Patterns in the cyanide stretching frequencies have been examined in several series of monometal- and CN{sup {minus}} bridged transition metal complexes. Metal-to-cyanide back-bonding can be identified as a major factor contributing to red shifts of v{sub CN} in monometal complexes. This effect is complicated in cyanide-bridged complexes in two ways: (a) when both metals can back-bond to cyanide, the net interaction is repulsive and results in a blue shift of v{sub CN}: and (b) when a donor and acceptor are bridged, V{sub CN} undergoes a substantial red shift (sometimes more than 60 cm{sup {minus}1} lower in energy than the parent monometal complex). These effects can be described by simple perturbational models for the electronic interactions. Monometal cyanide complexes and CN{sup {minus}}-bridged backbonding metals can be treated in terms of their perturbations of the CN{sup {minus}} {pi} and {pi}* orbitals by using a simple, Hueckel-like, three-center perturbational treatment of electronic interactions. However, bridged donor-acceptor pairs are best described by a vibronic model in which it is assumed that the extent of electronic delocalization is in equilibrium with variations of some nuclear coordinates. Consistent with this approach, it is found that (a) the oscillator strength of the donor-acceptor charge transfer (DACT) absorption is roughly proportional to the red shift of v{sub CN} and (b) there are strong symmetry constraints on the coupling.

  8. Swift Electrofluorochromism of Donor-Acceptor Conjugated Polytriphenylamines.

    PubMed

    Sun, Jingwei; Liang, Ziqi

    2016-07-20

    Electrofluorochromic (EFC) materials, which exhibit electrochemically controllable fluorescence, hold great promise in optoelectronic devices and biological analysis. Here we design such donor-acceptor (D-A) conjugated polymers-P(TPACO) and P(TCEC)-that contain the same electron-rich and oxidizable polytriphenylamine (PTPA) as π-backbone, yet with different electron-deficient ketone and cyano units as pendant groups, respectively. They both exhibit solvatochromic effects due to intrinsic characteristics of intramolecular charge transfer (ICT). Compared to P(TPACO), P(TCEC) shows stronger ICT, which leads to higher electrochemical oxidation potential and lower ion diffusion coefficient. Moreover, both polymers present simultaneous electrochromic (EC) and EFC behaviors with multistate display and remarkably rapid fluorescence response. The response time of P(TPACO) is as short as 0.19 s, nearly 4-fold faster than that of P(TCEC) (0.92 s). Such rapid response is found to be determined by the ion diffusion coefficient which is associated with the ICT nature. Finally, the EFC display device based on P(TPACO) is successfully demonstrated, which shows green fluorescence ON/OFF switching upon applied potentials. This work has successfully demonstrated that swift EFCs can be achieved by rational modulation of the ICT effect in such D-A conjugated polymers. PMID:27347724

  9. Benzodipyrrole-based Donor-Acceptor-type Boron Complexes as Tunable Near-infrared-Absorbing Materials.

    PubMed

    Nakamura, Tomoya; Furukawa, Shunsuke; Nakamura, Eiichi

    2016-07-20

    Benzodipyrrole-based donor-acceptor boron complexes were designed and synthesized as near-infrared-absorbing materials. The electron-rich organic framework combined with the Lewis acidic boron co-ordination enabled us to tune the LUMO energy level and the HOMO-LUMO gap (i.e.,the absorption wavelength) by changing the organic acceptor units, the number of boron atoms, and the substituents on the boron atoms. PMID:27311060

  10. Donor-Acceptor Complexes between Ammonia and Sulfur Trioxide: An FTIR and Computational Study.

    PubMed

    Haupa, Karolina; Bil, Andrzej; Mielke, Zofia

    2015-10-29

    The complexes of ammonia with sulfur trioxide have been studied using FTIR matrix isolation spectroscopy and DFT/B3LYP calculations with the aug-cc-pVTZ basis set. The NH3/SO3/Ar matrixes were prepared in two different ways. In one set of experiments the matrix was prepared by the simultaneous deposition of the NH3/Ar mixture and SO3 vapor from the thermal decomposition of K2S2O7. In the second set of experiments thermolysis products of sulfamic acid were trapped in an argon matrix. Both methods of matrix preparation led to the formation of the H3N·SO3 electron donor-acceptor complex that was characterized earlier. In the matrixes comprising thermolysis products of sulfamic acid, in addition to H3N·SO3, the H3N-SO3···NH3 complex (II(D)) was also identified. The identity of the complex was confirmed by comparison of the experimental and theoretical spectra of H3N-SO3···NH3 and D3N-SO3···ND3. The performed calculations show that in H3N-SO3···NH3 the two N atoms and the S atom are collinear; the two S-N bonds are nonequivalent, one is much shorter (2.230 Å) than the other one (2.852 Å). In the AIM topological analysis, the interaction energy decomposition and topological properties of the electron localizability indicator (ELI-D) allowed us to categorize the stronger N-S bond in the II(D) complex as a dative bond and to assume that the fragile N-S bond is a consequence of a weak electron-donor-acceptor interaction. The calculations indicate that the identified II(D) complex corresponds to a local minimum on the PES of the NH3/SO3 system of 2:1 stoichiometry. The (NH3)2SO3 complex, II(HB), corresponding to a global minimum is 7.95 kcal mol(-1) more stable than the II(D) complex. The reason that the II(D) complex is present in the matrix but not the II(HB) complex is discussed. PMID:26447490

  11. Efficient ambipolar transport properties in alternate stacking donor-acceptor complexes: from experiment to theory.

    PubMed

    Qin, Yunke; Cheng, Changli; Geng, Hua; Wang, Chao; Hu, Wenping; Xu, Wei; Shuai, Zhigang; Zhu, Daoben

    2016-05-18

    Comprehensive investigations of crystal structures, electrical transport properties and theoretical simulations have been performed over a series of sulfur-bridged annulene-based donor-acceptor complexes with an alternate stacking motif. A remarkably high mobility, up to 1.57 cm(2) V(-1) s(-1) for holes and 0.47 cm(2) V(-1) s(-1) for electrons, was obtained using organic single crystal field-effect transistor devices, demonstrating the efficient ambipolar transport properties. These ambipolar properties arise from the fact that the electronic couplings for both holes and electrons have the same super-exchange nature along the alternate stacking direction. The magnitude of super-exchange coupling depends not only on the intermolecular stacking distance and pattern, but also the energy level alignments between the adjacent donor-acceptor moieties. The concluded transport mechanism and structure-property relationship from this research will provide an important guideline for the future design of organic semiconductors based on donor-acceptor complexes. PMID:27157854

  12. Donor-acceptor type co-crystals of arylthio-substituted tetrathiafulvalenes and fullerenes.

    PubMed

    Lu, Xiaofeng; Sun, Jibin; Zhang, Shangxi; Ma, Longfei; Liu, Lei; Qi, Hui; Shao, Yongliang; Shao, Xiangfeng

    2015-01-01

    A series of donor-acceptor type co-crystals of fullerene (as the acceptor) and arylthio-substituted tetrathiafulvalene derivatives (Ar-S-TTF, as the donor) were prepared and their structural features were thoroughly investigated. The formation of co-crystals relies on the flexibility of Ar-S-TTF and the size matches between Ar-S-TTF and fullerene. Regarding their compositions, the studied co-crystals can be divided into two types, where types I and II have donor:acceptor ratios of 1:1 and 1:2, respectively. Multiple intermolecular interactions are observed between the donor and acceptor, which act to stabilize the structures of the resulting co-crystals. In the type I co-crystals, the fullerene molecule is surrounded by four Ar-S-TTF molecules, that is, two Ar-S-TTF molecules form a sandwich structure with one fullerene molecule and the other two Ar-S-TTF molecules interact with the fullerene molecule along their lateral axes. In the type II co-crystals, one fullerene molecule has the donor-acceptor mode similar to that in type I, whereas the other fullerene molecule is substantially surrounded by the aryl groups on Ar-S-TTF molecules and the solvent molecules. PMID:26199659

  13. How intermolecular geometrical disorder affects the molecular doping of donor-acceptor copolymers

    NASA Astrophysics Data System (ADS)

    di Nuzzo, Daniele; Fontanesi, Claudio; Jones, Rebecca; Allard, Sybille; Dumsch, Ines; Scherf, Ullrich; von Hauff, Elizabeth; Schumacher, Stefan; da Como, Enrico

    2015-03-01

    Molecular doping of conjugated polymers represents an important strategy for improving organic electronic devices. However, the widely reported low efficiency of doping remains a crucial limitation to obtain high performance. Here we investigate how charge transfer between dopant and donor-acceptor copolymers is affected by the spatial arrangement of the dopant molecule with respect to the copolymer repeat unit. We p-dope a donor-acceptor copolymer and probe its charge-sensitive molecular vibrations in films by infrared spectroscopy. We find that, compared with a related homopolymer, a four times higher dopant/polymer molar ratio is needed to observe signatures of charges. By DFT methods, we simulate the vibrational spectra, moving the dopant along the copolymer backbone and finding that efficient charge transfer occurs only when the dopant is close to the donor moiety. Our results show that the donor-acceptor structure poses an obstacle to efficient doping, with the acceptor moiety being inactive for p-type doping.

  14. Enhanced Charge Mobility in Polymer Nanocomposites Incorporating Donor-Acceptor Interfaces

    NASA Astrophysics Data System (ADS)

    Tameev, Alexey R.; Nikitenko, Vladimir R.; Vannikov, Anatoly V.

    2011-01-01

    Charge carrier transport in donor-acceptor (D-A) composites based on either poly(N-vinyl carbazole) or polyimide derivative incorporating either carbon single-walled nanotubes or nanocrystals of J-aggregated cyanine dyes is shown to exhibit a similar behavior. In the composite films, polymer/nanomaterial interface provides pathways of the high conductivity. Charge-transfer states (CTS) formed at the D-A interface are involved in the transport. The charge transport along the interface is suggested to arise due to the D-A integer charge transfer and strong interaction between adjacent opposite charges located on the donor and acceptor molecules. The approach based on the concept of sequence of charge carrier transfers through charge transfer states describes the increased electron and hole mobility in the composites. The approach predicts enhanced conductivity with reduced activation energy. Moreover, once the density of electron-hole pairs at the interface is rather high, significant part of the charge carriers can avoid hopping transport resulting in conductivity of metal type. The value of two-dimensional conductivity is estimated by numerical modeling.

  15. Synthesis and optoelectronic properties of Janus-dendrimer-type multivalent donor-acceptor systems.

    PubMed

    Dengiz, Cagatay; Breiten, Benjamin; Gisselbrecht, Jean-Paul; Boudon, Corinne; Trapp, Nils; Schweizer, W Bernd; Diederich, François

    2015-01-16

    A convergent, multistep protocol was employed for the synthesis of a Janus-type multivalent donor-acceptor system. The synthetic approach is based on a Sonogashira cross-coupling of two differently ferrocene-(Fc) substituted dendrons and a final sixfold [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reaction with tetracyanoethene, which occurs regioselectively at only one of the rigidly linked dendrons. The structural and optoelectronic properties of the compounds were investigated by X-ray analysis, UV/vis spectroscopy, and electrochemistry. The target Janus-system displays redox-amphoteric behavior. The nonalkynylated Fc end groups in one dendron are readily and reversibly oxidized. The second dendron, in which the terminal Fc-activated alkynes underwent the CA-RE reaction to give tetracyanobuta-1,3-dienes in the final step of the synthesis, undergoes four reversible 3-e(-) reductions in the very narrow potential range of 1 V. A spontaneous intramolecular charge transfer from the donor into the acceptor hemisphere was not observed. Furthermore, the oxidation potential of the Fc donors in one hemisphere is hardly perturbed by the push-pull acceptors in the other, which suggests that electronic communication along the π-system, with several meta-connectivities, is not efficient. Therefore, the charge-transfer bands seen in the Janus-type system originate from the interaction of the Fc donors with the directly connected tetracyanobuta-1,3-diene acceptors in the same hemisphere. PMID:25489964

  16. Solvent-tuned intramolecular charge-recombination rates in a conjugated donor-acceptor molecule

    NASA Technical Reports Server (NTRS)

    Khundkar, Lutfur R.; Stiegman, A. E.; Perry, Joseph W.

    1990-01-01

    The nonradiative charge-recombination rates from the charge-transfer state of a new conjugated donor-acceptor molecule (p-cyano-p-prime-methylthiodiphenylacetylene) can be tuned over almost an order of magnitude by varying the polarity of the solvent. These measurements of intramolecular recombination show a turnover of rates as a function of emission energy, consistent with the 'normal' and 'inverted' behavior of Marcus theory. Steady-state spectra and time-resolved measurements make it possible to quantitatively compare thermal and optical electron-transfer rates as a function of driving force and demonstrate their correspondence.

  17. Vacancy compensation and related donor-acceptor pair recombination in bulk AlN

    SciTech Connect

    Gaddy, BE; Bryan, Z; Bryan, I; Kirste, R; Xie, JQ; Dalmau, R; Moody, B; Kumagai, Y; Nagashima, T; Kubota, Y; Kinoshita, T; Koukitu, A; Sitar, Z; Collazo, R; Irving, DL

    2013-10-14

    A prominent 2.8 eV emission peak is identified in bulk AlN substrates grown by physical vapor transport. This peak is shown to be related to the carbon concentration in the samples. Density functional theory calculations predict that this emission is caused by a donor-acceptor pair (DAP) recombination between substitutional carbon on the nitrogen site and a nitrogen vacancy. Photoluminescence and photoluminescence-excitation spectroscopy are used to confirm the model and indicate the DAP character of the emission. The interaction between defects provides a pathway to creating ultraviolet-transparent AlN substrates for optoelectronics applications. (C) 2013 AIP Publishing LLC.

  18. Intramolecular charge transfer in donor-acceptor molecules

    SciTech Connect

    Slama-Schwok, A.; Blanchard-Desce, M.; Lehn, J.M. )

    1990-05-17

    The photophysical properties of donor-acceptor molecules, push-pull polyenes and carotenoids, have been studied by absorption and fluorescence spectroscopy. The compounds bear various acceptor and donor groups, linked together by chains of different length and structure. The position of the absorption and fluorescence maxima and their variation in solvents of increasing polarity are in agreement with long-distance intramolecular charge-transfer processes, the linker acting as a molecular wire. The effects of the linker length and structure and of the nature of acceptor and donor are presented.

  19. Unraveling the Photoswitching Mechanism in Donor-Acceptor Stenhouse Adducts.

    PubMed

    Lerch, Michael M; Wezenberg, Sander J; Szymanski, Wiktor; Feringa, Ben L

    2016-05-25

    Molecular photoswitches have opened up a myriad of opportunities in applications ranging from responsive materials and control of biological function to molecular logics. Here, we show that the photoswitching mechanism of donor-acceptor Stenhouse adducts (DASA), a recently reported class of photoswitches, proceeds by photoinduced Z-E isomerization, followed by a thermal, conrotatory 4π-electrocyclization. The photogenerated intermediate is manifested by a bathochromically shifted band in the visible absorption spectrum of the DASA. The identification of the role of this intermediate reveals a key step in the photoswitching mechanism that is essential to the rational design of switching properties via structural modification. PMID:27152878

  20. Donor-acceptor chemistry in the main group.

    PubMed

    Rivard, Eric

    2014-06-21

    This Perspective article summarizes recent progress from our laboratory in the isolation of reactive main group species using a general donor-acceptor protocol. A highlight of this program is the use of carbon-based donors in combination with suitable Lewis acidic acceptors to yield stable complexes of parent Group 14 element hydrides (e.g. GeH2 and H2SiGeH2). It is anticipated that this strategy could be extended to include new synthetic targets from throughout the Periodic Table with possible applications in bottom-up materials synthesis and main group element catalysis envisioned. PMID:24788390

  1. Quantifying charge transfer energies at donor-acceptor interfaces in small-molecule solar cells with constrained DFTB and spectroscopic methods.

    PubMed

    Scholz, Reinhard; Luschtinetz, Regina; Seifert, Gotthard; Jägeler-Hoheisel, Till; Körner, Christian; Leo, Karl; Rapacioli, Mathias

    2013-11-27

    Charge transfer states around the donor-acceptor interface in an organic solar cell determine the device performance in terms of the open circuit voltage. In the present work, we propose a computational scheme based on constrained density functional tight binding theory (c-DFTB) to assess the energy of the lowest charge transfer (CT) state in such systems. A comparison of the c-DFTB scheme with Hartree-Fock based configuration interaction of singles (CIS) and with time-dependent density functional theory (TD-DFT) using the hybrid functional B3LYP reveals that CIS and c-DFTB reproduce the correct Coulomb asymptotics between cationic donor and anionic acceptor configurations, whereas TD-DFT gives a qualitatively wrong excitation energy. Together with an embedding scheme accounting for the polarizable medium, this c-DFTB scheme is applied to several donor-acceptor combinations used in molecular solar cells. The external quantum efficiency of photovoltaic cells based on zinc phthalocyanine-C60 blends reveals a CT band remaining much narrower than the density of states of acceptor HOMO and donor LUMO, an observation which can be interpreted in a natural way in terms of Marcus transfer theory. A detailed comparison with c-DFTB calculations reveals an energy difference of 0.32 eV between calculated and observed absorption from the electronic ground state into the CT state. In a blend of a functionalized thiophene and C60, the photoluminescence spectra differ significantly from neat films, allowing again an assignment to CT states. The proposed computational scheme reproduces the observed trends of the observed open circuit voltages in photovoltaic devices relying on several donor-acceptor blends, finding an offset of 1.16 eV on average. This value is similar as in polymer-fullerene photovoltaic systems where it amounts to about 0.9 eV, indicating that the photophysics of CT states in molecular donor-acceptor blends and in polymer-fullerene blends are governed by the

  2. Quantifying charge transfer energies at donor-acceptor interfaces in small-molecule solar cells with constrained DFTB and spectroscopic methods

    NASA Astrophysics Data System (ADS)

    Scholz, Reinhard; Luschtinetz, Regina; Seifert, Gotthard; Jägeler-Hoheisel, Till; Körner, Christian; Leo, Karl; Rapacioli, Mathias

    2013-11-01

    Charge transfer states around the donor-acceptor interface in an organic solar cell determine the device performance in terms of the open circuit voltage. In the present work, we propose a computational scheme based on constrained density functional tight binding theory (c-DFTB) to assess the energy of the lowest charge transfer (CT) state in such systems. A comparison of the c-DFTB scheme with Hartree-Fock based configuration interaction of singles (CIS) and with time-dependent density functional theory (TD-DFT) using the hybrid functional B3LYP reveals that CIS and c-DFTB reproduce the correct Coulomb asymptotics between cationic donor and anionic acceptor configurations, whereas TD-DFT gives a qualitatively wrong excitation energy. Together with an embedding scheme accounting for the polarizable medium, this c-DFTB scheme is applied to several donor-acceptor combinations used in molecular solar cells. The external quantum efficiency of photovoltaic cells based on zinc phthalocyanine-C60 blends reveals a CT band remaining much narrower than the density of states of acceptor HOMO and donor LUMO, an observation which can be interpreted in a natural way in terms of Marcus transfer theory. A detailed comparison with c-DFTB calculations reveals an energy difference of 0.32 eV between calculated and observed absorption from the electronic ground state into the CT state. In a blend of a functionalized thiophene and C60, the photoluminescence spectra differ significantly from neat films, allowing again an assignment to CT states. The proposed computational scheme reproduces the observed trends of the observed open circuit voltages in photovoltaic devices relying on several donor-acceptor blends, finding an offset of 1.16 eV on average. This value is similar as in polymer-fullerene photovoltaic systems where it amounts to about 0.9 eV, indicating that the photophysics of CT states in molecular donor-acceptor blends and in polymer-fullerene blends are governed by the same

  3. Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study

    SciTech Connect

    Fonari, A.; Corbin, N. S.; Coropceanu, V. E-mail: coropceanu@gatech.edu; Vermeulen, D.; McNeil, L. E.; Goetz, K. P.; Jurchescu, O. D.; Bredas, J. L. E-mail: coropceanu@gatech.edu

    2015-12-14

    We establish a reliable quantum-mechanical approach to evaluate the vibrational properties of donor-acceptor molecular crystals. The anthracene-PMDA (PMDA = pyromellitic dianhydride) crystal, where anthracene acts as the electron donor and PMDA as the electron acceptor, is taken as a representative system for which experimental non-resonance Raman spectra are also reported. We first investigate the impact that the amount of nonlocal Hartree-Fock exchange (HFE) included in a hybrid density functional has on the geometry, normal vibrational modes, electronic coupling, and electron-vibrational (phonon) couplings. The comparison between experimental and theoretical Raman spectra indicates that the results based on the αPBE functional with 25%-35% HFE are in better agreement with the experimental results compared to those obtained with the pure PBE functional. Then, taking αPBE with 25% HFE, we assign the vibrational modes and examine their contributions to the relaxation energy related to the nonlocal electron-vibration interactions. The results show that the largest contribution (about 90%) is due to electron interactions with low-frequency vibrational modes. The relaxation energy in anthracene-PMDA is found to be about five times smaller than the electronic coupling.

  4. Donor-acceptor complexation and dehydrogenation chemistry of aminoboranes.

    PubMed

    Malcolm, Adam C; Sabourin, Kyle J; McDonald, Robert; Ferguson, Michael J; Rivard, Eric

    2012-12-01

    A series of formal donor-acceptor adducts of aminoborane (H(2)BNH(2)) and its N-substituted analogues (H(2)BNRR') were prepared: LB-H(2)BNRR'(2)-BH(3) (LB = DMAP, IPr, IPrCH(2) and PCy(3); R and R' = H, Me or tBu; IPr = [(HCNDipp)(2)C:] and Dipp = 2,6-iPr(2)C(6)H(3)). To potentially access complexes of molecular boron nitride, LB-BN-LA (LA = Lewis acid), preliminary dehydrogenation chemistry involving the parent aminoborane adducts LB-H(2)BNH(2)-BH(3) was investigated using [Rh(COD)Cl](2), CuBr, and NiBr(2) as dehydrogenation catalysts. In place of isolating the intended dehydrogenated BN donor-acceptor complexes, the formation of borazine was noted as a major product. Attempts to prepare the fluoroarylborane-capped aminoborane complexes, LB-H(2)BNH(2)-B(C(6)F(5))(3), are also described. PMID:23153209

  5. The role of amino acid electron-donor/acceptor atoms in host-cell binding peptides is associated with their 3D structure and HLA-binding capacity in sterile malarial immunity induction

    SciTech Connect

    Patarroyo, Manuel E.; Almonacid, Hannia; Moreno-Vranich, Armando

    2012-01-20

    Highlights: Black-Right-Pointing-Pointer Fundamental residues located in some HABPs are associated with their 3D structure. Black-Right-Pointing-Pointer Electron-donor atoms present in {beta}-turn, random, distorted {alpha}-helix structures. Black-Right-Pointing-Pointer Electron-donor atoms bound to HLA-DR53. Black-Right-Pointing-Pointer Electron-acceptor atoms present in regular {alpha}-helix structure bound to HLA-DR52. -- Abstract: Plasmodium falciparum malaria continues being one of the parasitic diseases causing the highest worldwide mortality due to the parasite's multiple evasion mechanisms, such as immunological silence. Membrane and organelle proteins are used during invasion for interactions mediated by high binding ability peptides (HABPs); these have amino acids which establish hydrogen bonds between them in some of their critical binding residues. Immunisation assays in the Aotus model using HABPs whose critical residues had been modified have revealed a conformational change thereby enabling a protection-inducing response. This has improved fitting within HLA-DR{beta}1{sup Asterisk-Operator} molecules where amino acid electron-donor atoms present in {beta}-turn, random or distorted {alpha}-helix structures preferentially bound to HLA-DR53 molecules, whilst HABPs having amino acid electron-acceptor atoms present in regular {alpha}-helix structure bound to HLA-DR52. This data has great implications for vaccine development.

  6. Nanostructured donor-acceptor self assembly with improved photoconductivity.

    PubMed

    Saibal, B; Ashar, A Z; Devi, R Nandini; Narayan, K S; Asha, S K

    2014-11-12

    Nanostructured supramolecular donor-acceptor assemblies were formed when an unsymmetrical N-substituted pyridine functionalized perylenebisimide (UPBI-Py) was complexed with oligo(p-phenylenevinylene) (OPVM-OH) complementarily functionalized with hydroxyl unit and polymerizable methacrylamide unit at the two termini. The resulting supramolecular complex [UPBI-Py (OPVM-OH)]1.0 upon polymerization by irradiation in the presence of photoinitiator formed well-defined supramolecular polymeric nanostructures. Self-assembly studies using fluorescence emission from thin film samples showed that subtle structural changes occurred on the OPV donor moiety following polymerization. The 1:1 supramolecular complex showed red-shifted aggregate emission from both OPV (∼500 nm) and PBI (∼640 nm) units, whereas the OPV aggregate emission was replaced by intense monomeric emission (∼430 nm) upon polymerizing the methacrylamide units on the OPVM-OH. The bulk structure was studied using wide-angle X-ray diffraction (WXRD). Complex formation resulted in distinct changes in the cell parameters of OPVM-OH. In contrast, a physical mixture of 1 mol each of OPVM-OH and UPBI-Py prepared by mixing the powdered solid samples together showed only a combination of reflections from both parent molecules. Thin film morphology of the 1:1 molecular complex as well as the supramolecular polymer complex showed uniform lamellar structures in the domain range <10 nm. The donor-acceptor supramolecular complex [UPBI-Py (OPVM-OH)]1.0 exhibited space charge limited current (SCLC) with a bulk mobility estimate of an order of magnitude higher accompanied by a higher photoconductivity yield compared to the pristine UPBI-Py. This is a very versatile method to obtain spatially defined organization of n and p-type semiconductor materials based on suitably functionalized donor and acceptor molecules resulting in improved photocurrent response using self-assembly. PMID:25283356

  7. Identification of photoluminescence bands in AlGaAs/InGaAs/GaAs PHEMT heterostructures with donor-acceptor-doped barriers

    SciTech Connect

    Gulyaev, D. V. Zhuravlev, K. S.; Bakarov, A. K.; Toropov, A. I.

    2015-02-15

    The photoluminescence of AlGaAs/InGaAs/GaAs pseudomorphic high-electron mobility transistor heterostructures with donor-acceptor-doped AlGaAs barriers is studied. It is found that the introduction of additional p{sup +}-doped AlGaAs layers into the design brings about the appearance of new bands in the photoluminescence spectra. These bands are identified as resulting from transitions (i) in donor-acceptor pairs in doped AlGaAs layers and (ii) between the conduction subband and acceptor levels in the undoped InGaAs quantum well.

  8. Alternative Donor--Acceptor Stacks from Crown Ethers and Naphthalene Diimide Derivatives: Rapid, Selective Formation from Solution and Solid State Grinding

    SciTech Connect

    Advanced Light Source; Liu, Yi; Klivansky, Liana; Cao, Dennis; Snauko, Marian; Teat, Simon J.; Struppe, Jochem O.; Koshkakaryan, Gayane

    2009-01-22

    Self assembling {pi}-conjugated molecules into ordered structures are of increasing interest in the field of organic electronics. One particular example is charge transfer complexes containing columnar alternative donor-acceptor (ADA) stacks, where neutral and ionic ground states can be readily tuned to modulate electrical, optical, and ferroelectrical properties. Aromatic-aromatic and charge transfer interactions have been the leading driving forces in assisting the self-assembly of ADA stacks. Various folding structures containing ADA stacks were assembled in solution with the aid of solvophobic or ion-binding interactions. Meanwhile, examples of solid ADA stacks, which are more appealing for practical use in devices, were obtained from cocrystalization of binary components or mesophase assembly of liquid crystals in bulk blends. Regardless of these examples, faster and more controllable approaches towards precise supramolecular order in the solid state are still highly desirable.

  9. Design, synthesis and study of supramolecular donor-acceptor systems mimicking natural photosynthesis processes

    NASA Astrophysics Data System (ADS)

    Bikram, Chandra

    This dissertation investigates the chemical ingenuity into the development of various photoactive supramolecular donor -- acceptor systems to produce clean and carbon free energy for the next generation. The process is inspired by the principles learned from nature's approach where the solar energy is converted into the chemical energy through the natural photosynthesis process. Owing to the importance and complexity of natural photosynthesis process, we have designed ideal donor-acceptor systems to investigate their light energy harvesting properties. This process involves two major steps: the first step is the absorption of light energy by antenna or donor systems to promote them to an excited electronic state. The second step involves, the transfer of excitation energy to the reaction center, which triggers an electron transfer process within the system. Based on this principle, the research is focused into the development of artificial photosynthesis systems to investigate dynamics of photo induced energy and electron transfer events. The derivatives of Porphyrins, Phthalocyanines, BODIPY, and SubPhthalocyanines etc have been widely used as the primary building blocks for designing photoactive and electroactive ensembles in this area because of their excellent and unique photophysical and photochemical properties. Meanwhile, the fullerene, mainly its readily available version C60 is typically used as an electron acceptor component because of its unique redox potential, symmetrical shape and low reorganization energy appropriate for improved charge separation behavior. The primary research motivation of the study is to achieve fast charge separation and slow charge recombination of the system by stabilizing the radical ion pairs which are formed from photo excitation, for maximum utility of solar energy. Besides Fullerene C60, this dissertation has also investigated the potential application of carbon nanomaterials (Carbon nanotubes and graphene) as primary

  10. Structural control of donor-acceptor mechanically interlocked molecules and supramolecular complexes

    NASA Astrophysics Data System (ADS)

    Friedman, Douglas Cary

    aided the structural analysis, are described. The final chapter describes how to control the secondary structure of donor-acceptor oligorotaxanes in which electron-poor tetracationic cyclophanes encircle electron-rich aromatic recognition sites linked by polyether chains. Design aspects, including built-in [pi···pi] stacking and [C--H···O] and [C--H···pi] interactions, are critical to ensure the discrete, extended secondary structures envisioned in the design and which are evidenced by comprehensive 1H NMR spectroscopic analyses.

  11. Proton Donor/acceptor Propensities of Ammonia: Rotational Studies of its Molecular Complexes with Organic Molecules

    NASA Astrophysics Data System (ADS)

    Giuliano, Barbara M.; Maris, Assimo; Melandri, Sonia; Favero, Laura B.; Evangelisti, Luca; Caminati, Walther

    2009-06-01

    We studied the rotational spectra of the adducts of ammonia with several organic molecules, namely tert-butanol, glycidol, ethyl alcohol, anisol and 1,4-difluorobenzene. The adducts with glycidol and ethanol have been observed for both conformers of the substrate molecule. Based on the rotational and ^{14}N quadrupole coupling constants of the various complexes, we found a considerably different behaviour of ammonia, with respect to water, in its proton donor/acceptor double role. In the interaction with the three alcohol molecules, NH_{3} acts as a proton acceptor and the OH groups as a proton donor. However, in the case of glycidol-NH_{3}, a secundary N-H\\cdotsO interaction occurrs between ammonia and the ether oxygen. This interaction generates a sizable V_{3} barrier to the internal rotation of the NH_{3} moiety, while NH_{3} undergoes a free rotation in tert-butanol-NH_{3} and in ethanol-NH_{3}. As to the anisole-NH_{3} and 1,4-difluorobenzene-NH_{3} complexes, the NH_{3} group explicits its double proton donor/acceptor role, although through two weak (C_{Me}-H\\cdotsN and N-H\\cdotsπ) H-bonds. There is, however, an important difference between the two complexes, because in the first one NH_{3} lies out of the aromatic plane, while in the second one it is in the plane of the aromatic ring. B. M. Giuliano, M. C. Castrovilli, A. Maris, S. Melandri, W. Caminati and E. A. Cohen, Chem.Phys.Lett., 2008, 463, 330 B. M. Giuliano, S. Melandri, A. Maris, L. B. Favero and W. Caminati, Angew.Chem.Int.Ed., 2009, 48, 1102

  12. Stimuli-Responsive Reversible Fluorescence Switching in a Crystalline Donor-Acceptor Mixture Film: Mixed Stack Charge-Transfer Emission versus Segregated Stack Monomer Emission.

    PubMed

    Park, Sang Kyu; Cho, Illhun; Gierschner, Johannes; Kim, Jin Hong; Kim, Jong H; Kwon, Ji Eon; Kwon, Oh Kyu; Whang, Dong Ryeol; Park, Jung-Hwa; An, Byeong-Kwan; Park, Soo Young

    2016-01-01

    We report on a molecularly tailored 1:1 donor-acceptor (D-A) charge-transfer (CT) cocrystal that manifests strongly red-shifted CT luminescence characteristics, as well as noteworthy reconfigurable self-assembling behaviors. A loosely packed molecular organization is obtained as a consequence of the noncentrosymmetric chemical structure of molecule A1, which gives rise to considerable free volume and weak intermolecular interactions. The stacking features of the CT complex result in an external stimuli-responsive molecular stacking reorganization between the mixed and demixed phases of the D-A pair. Accordingly, high-contrast fluorescence switching (red↔blue) is realized on the basis of the strong alternation of the electronic properties between the mixed and demixed phases. A combination of structural, spectroscopic, and computational studies reveal the underlying mechanism of this stimuli-responsive behavior. PMID:26585755

  13. News from the Periodic Table: An Introduction to "Periodicity Symbols, Tables, and Models for Higher-Order Valency and Donor-Acceptor Kinships"

    ERIC Educational Resources Information Center

    Bent, Henry A.; Weinhold, Frank

    2007-01-01

    The study presents and explains the various periodicity symbols, tables and models for the higher-order valency and donor-acceptor kinships used in chemistry. The described alternative tables are expected to improve the pedagogical consistency of the chemical periodicity patterns with better electronic behavior.

  14. A design strategy for intramolecular singlet fission mediated by charge-transfer states in donor-acceptor organic materials

    NASA Astrophysics Data System (ADS)

    Busby, Erik; Xia, Jianlong; Wu, Qin; Low, Jonathan Z.; Song, Rui; Miller, John R.; Zhu, X.-Y.; Campos, Luis M.; Sfeir, Matthew Y.

    2015-04-01

    The ability to advance our understanding of multiple exciton generation (MEG) in organic materials has been restricted by the limited number of materials capable of singlet fission. A particular challenge is the development of materials that undergo efficient intramolecular fission, such that local order and strong nearest-neighbour coupling is no longer a design constraint. Here we address these challenges by demonstrating that strong intrachain donor-acceptor interactions are a key design feature for organic materials capable of intramolecular singlet fission. By conjugating strong-acceptor and strong-donor building blocks, small molecules and polymers with charge-transfer states that mediate population transfer between singlet excitons and triplet excitons are synthesized. Using transient optical techniques, we show that triplet populations can be generated with yields up to 170%. These guidelines are widely applicable to similar families of polymers and small molecules, and can lead to the development of new fission-capable materials with tunable electronic structure, as well as a deeper fundamental understanding of MEG.

  15. A design strategy for intramolecular singlet fission mediated by charge-transfer states in donor-acceptor organic materials.

    PubMed

    Busby, Erik; Xia, Jianlong; Wu, Qin; Low, Jonathan Z; Song, Rui; Miller, John R; Zhu, X-Y; Campos, Luis M; Sfeir, Matthew Y

    2015-04-01

    The ability to advance our understanding of multiple exciton generation (MEG) in organic materials has been restricted by the limited number of materials capable of singlet fission. A particular challenge is the development of materials that undergo efficient intramolecular fission, such that local order and strong nearest-neighbour coupling is no longer a design constraint. Here we address these challenges by demonstrating that strong intrachain donor-acceptor interactions are a key design feature for organic materials capable of intramolecular singlet fission. By conjugating strong-acceptor and strong-donor building blocks, small molecules and polymers with charge-transfer states that mediate population transfer between singlet excitons and triplet excitons are synthesized. Using transient optical techniques, we show that triplet populations can be generated with yields up to 170%. These guidelines are widely applicable to similar families of polymers and small molecules, and can lead to the development of new fission-capable materials with tunable electronic structure, as well as a deeper fundamental understanding of MEG. PMID:25581625

  16. Synthesis, Structure, and Optical Studies of Donor-Acceptor-Type Near-Infrared (NIR) Aza-Boron-Dipyrromethene (BODIPY) Dyes.

    PubMed

    Balsukuri, Naresh; Lone, Mohsin Y; Jha, Prakash C; Mori, Shigeki; Gupta, Iti

    2016-05-20

    Six donor-acceptor-type near-infrared (NIR) aza-boron-dipyrromethene (BODIPY) dyes and their corresponding aza-dipyrrins were designed and synthesized. The donor moieties at the 1,7-positions of the aza-BODIPY core were varied from naphthyl to N-phenylcarbazole to N-butylcarbazole. The 3,5-positions were also substituted with phenyl or thienyl groups in the aza-BODIPYs. Photophysical, electrochemical, and computational studies were carried out. The absorption and emission spectra of aza-BODIPYs were significantly redshifted (≈100 nm) relative to the parent tetraphenylaza-BODIPY. Fluorescence studies suggested effective energy transfer (up to 93 %) from donor groups to the aza-BODIPY core in all of the compounds under study. Time-dependent (TD)-DFT studies indicated effective electronic interactions between energy donor groups and aza-dipyrrin unit in all the aza-BODIPYs studied. The HOMO-LUMO gap (ΔE) calculated from cyclic voltammetry data was found to be lower for six aza-BODIPYs relative to their corresponding aza-dipyrrins. PMID:26918806

  17. The effect of memory in the stochastic master equation analyzed using the stochastic Liouville equation of motion. Electronic energy migration transfer between reorienting donor-donor, donor-acceptor chromophores

    NASA Astrophysics Data System (ADS)

    Håkansson, Pär; Westlund, Per-Olof

    2005-01-01

    This paper discusses the process of energy migration transfer within reorientating chromophores using the stochastic master equation (SME) and the stochastic Liouville equation (SLE) of motion. We have found that the SME over-estimates the rate of the energy migration compared to the SLE solution for a case of weakly interacting chromophores. This discrepancy between SME and SLE is caused by a memory effect occurring when fluctuations in the dipole-dipole Hamiltonian ( H( t)) are on the same timescale as the intrinsic fast transverse relaxation rate characterized by (1/ T2). Thus the timescale critical for energy-transfer experiments is T2≈10 -13 s. An extended SME is constructed, accounting for the memory effect of the dipole-dipole Hamiltonian dynamics. The influence of memory on the interpretation of experiments is discussed.

  18. The effect of memory in the stochastic master equation analyzed using the stochastic Liouville equation of motion. Electronic energy migration transfer between reorienting donor-donor, donor-acceptor chromophores.

    PubMed

    Håkansson, Pär; Westlund, Per-Olof

    2005-01-01

    This paper discusses the process of energy migration transfer within reorientating chromophores using the stochastic master equation (SME) and the stochastic Liouville equation (SLE) of motion. We have found that the SME over-estimates the rate of the energy migration compared to the SLE solution for a case of weakly interacting chromophores. This discrepancy between SME and SLE is caused by a memory effect occurring when fluctuations in the dipole-dipole Hamiltonian (H(t)) are on the same timescale as the intrinsic fast transverse relaxation rate characterized by (1/T(2)). Thus the timescale critical for energy-transfer experiments is T(2) approximately 10(-13) s. An extended SME is constructed, accounting for the memory effect of the dipole-dipole Hamiltonian dynamics. The influence of memory on the interpretation of experiments is discussed. PMID:15556453

  19. Synthesis, photophysical properties of triazolyl-donor/acceptor chromophores decorated unnatural amino acids: Incorporation of a pair into Leu-enkephalin peptide and application of triazolylperylene amino acid in sensing BSA.

    PubMed

    Bag, Subhendu Sekhar; Jana, Subhashis; Pradhan, Manoj Kumar

    2016-08-15

    The research in the field of design and synthesis of unnatural amino acids is growing at a fast space for the increasing demand of proteins of potential therapeutics and many other diversified novel functional applications. Thus, we report herein the design and synthesis of microenvironment sensitive fluorescent triazolyl unnatural amino acids (UNAA) decorated with donor and/or acceptor aromatic chromophores via click chemistry. The synthesized fluorescent amino acids show interesting solvatochromic characteristic and/or intramolecular charge transfer (ICT) feature as is revealed from the UV-visible, fluorescence photophysical properties and DFT/TDDFT calculation. HOMO-LUMO distribution shows that the emissive states of some of the amino acids are characterized with more significant electron redistribution between the triazolyl moiety and the aromatic chromophores linked to it leading to modulated emission property. A pair of donor-acceptor amino acid shows interesting photophysical interaction property indicating a FRET quenching event. Furthermore, one of the amino acid, triazolyl-perylene amino acid, has been exploited for studying interaction with BSA and found that it is able to sense BSA with an enhancement of fluorescence intensity. Finally, we incorporated a pair of donor/acceptor amino acids into a Leu-enkephalin analogue pentapeptide which was found to adopt predominantly type II β-turn conformation. We envisage that our investigation is of importance for the development of new fluorescent donor-acceptor unnatural amino acids a pair of which can be exploited for generating fluorescent peptidomimetic probe of interesting photophysical property for applications in studying peptide-protein interaction. PMID:27372839

  20. Donor-acceptor star-shaped conjugated macroelectrolytes: synthesis, light-harvesting properties, and self-assembly-induced Förster resonance energy transfer.

    PubMed

    Zhao, Li; Liu, Cheng-Fang; Xu, Wei-Dong; Jiang, Yi; Lai, Wen-Yong; Huang, Wei

    2015-06-01

    A novel series of donor-acceptor star-shaped conjugated macroelectrolytes (CMEs), denoted as 4FTs, including anionic carboxylic acid sodium groups (4FNaT), neutral diethanolamine groups (4FNOHT), and cationic ammonium groups (4FNBrT), were designed, synthesized, and explored as an excellent platform to investigate the impact of various polar pendent groups on self-assembly behaviors. The resulting CMEs with donor-acceptor star-shaped architectures exhibited distinct light-harvesting properties. The interactions between 4FTs and TrNBr, a star-shaped monodisperse CME grafted with cationic quaternary ammonium side chains, were investigated in H2O and CH3OH using steady-state, time-resolved fluorescence, dynamic light scattering (DLS), and transmission electron microscopy (TEM). Highly favored energy transfer has been proven by the excellent spectral overlap between TrNBr fluorescence and 4FTs absorptions which can be tuned by adjusting the pendent polar groups and solvents. It is suggested that self-assembled structures are formed between TrNBr and 4FNaT, while there is no obvious change for TrNBr/4FNOHT and TrNBr/4FNBrT in both H2O and CH3OH at low concentrations (<10(-6) M). This result is confirmed by the change of the TrNBr and 4FTs fluorescence properties and the time-resolved fluorescence data. The overall results manifest that at low concentrations the self-assembly between TrNBr and 4FTs is dominated by the electrostatic interactions. This study suggests that the functionalization of pendent polar groups of star-shaped CMEs has proven to be effective to modulate the self-assembly behaviors in dilute solutions and thus provide a strategy to further manage the optoelectronic properties. PMID:25981514

  1. Interfacial Donor-Acceptor Engineering of Nanofiber Materials To Achieve Photoconductivity and Applications.

    PubMed

    Zang, Ling

    2015-10-20

    Self-assembly of π-conjugate molecules often leads to formation of well-defined nanofibril structures dominated by the columnar π-π stacking between the molecular planes. These nanofibril materials have drawn increasing interest in the research frontiers of nanomaterials and nanotechnology, as the nanofibers demonstrate one-dimensionally enhanced exciton and charge diffusion along the long axis, and present great potential for varying optoelectronic applications, such as sensors, optics, photovoltaics, and photocatalysis. However, poor electrical conductivity remains a technical drawback for these nanomaterials. To address this problem, we have developed a series of nanofiber structures modified with different donor-acceptor (D-A) interfaces that are tunable for maximizing the photoinduced charge separation, thus leading to increase in the electrical conductivity. The D-A interface can be constructed with covalent linker or noncovalent interaction (e.g., hydrophobic interdigitation between alkyl chains). The noncovalent method is generally more flexible for molecular design and solution processing, making it more adaptable to be applied to other fibril nanomaterials such as carbon nanotubes. In this Account, we will discuss our recent discoveries in these research fields, aiming to provide deep insight into the enabling photoconductivity of nanofibril materials, and the dependence on interface structure. The photoconductivity generated with the nanofibril material is proportional to the charge carriers density, which in turn is determined by the kinetics balance of the three competitive charge transfer processes: (1) the photoinduced electron transfer from D to A (also referred to as exciton dissociation), generating majority charge carrier located in the nanofiber; (2) the back electron transfer; and (3) the charge delocalization along the nanofiber mediated by the π-π stacking interaction. The relative rates of these charge transfer processes can be tuned by

  2. Tuning the Rainbow: Systematic Modulation of Donor-Acceptor Systems through Donor Substituents and Solvent.

    PubMed

    Larsen, Christopher B; van der Salm, Holly; Shillito, Georgina E; Lucas, Nigel T; Gordon, Keith C

    2016-09-01

    A series of donor-acceptor compounds is reported in which the energy of the triarylamine donor is systematically tuned through para substitution with electron-donating methoxy and electron-withdrawing cyano groups. The acceptor units investigated are benzothiadiazole (btd), dipyridophenazine (dppz), and its [ReCl(CO)3(dppz)] complex. The effect of modulating donor energy on the electronic and photophysical properties is investigated using (1)H NMR spectroscopy, DFT calculations, electrochemistry, electronic absorption and emission spectroscopies, ground state and resonance Raman spectroscopy, and transient absorption spectroscopy. Qualitative correlations between the donor energy and the properties of interest are obtained using Hammett σ(+) constants. Methoxy and cyano groups are shown to destabilize and stabilize, respectively, the frontier molecular orbitals, with the HOMO affected more significantly than the LUMO, narrowing the HOMO-LUMO band gap as the substituent becomes more electron-donating-observable as a bathochromic shift in low-energy charge-transfer absorption bands. Charge-transfer emission bands are also dependent on the electron-donating/withdrawing nature of the substituent, and in combination with the highly solvatochromic nature of charge-transfer states, emission can be tuned to span the entire visible region. PMID:27500590

  3. Combined impact of entropy and carrier delocalization on charge transfer exciton dissociation at the donor-acceptor interface

    NASA Astrophysics Data System (ADS)

    Ono, Shota; Ohno, Kaoru

    2016-08-01

    Several models of the charge transfer exciton (CTE) have been proposed to explain its dissociation at the donor-acceptor (DA) interface. However, the underlying physics is still under debate. Here, we derive a temperature (T ) dependent tight-binding model for an electron-hole pair at the DA interface. The main finding is the existence of the localization-delocalization transition at a critical T , which can explain the CTE dissociation. The present study highlights the combined effect of entropy (finite T ) and carrier delocalization in the CTE dissociation.

  4. High Resolution Stark Spectroscopy of Model Donor-Acceptor Aminobenzonitriles in the Gas Phase.

    NASA Astrophysics Data System (ADS)

    Fleisher, Adam J.; Clements, Casey L.; Bird, Ryan G.; Pratt, David W.; Alvarez-Valtierra, Leonardo

    2011-06-01

    Electronic communication between donor-acceptor systems is prevalent in many chemical processes. Unfortunately, an accurate description of the changes in molecular geometry responsible for intramolecular charge transfer (ICT) is difficult to ascertain. Reported here are the S0, LA, and LB electronic state structures and dipole moments of two model ICT systems, 4-(1H-pyrrol-l-yl)benzonitrile (PBN) and 4-(1-pyrrolidinyl)benzonitrile (PDBN), as measured by rotationally resolved electronic spectroscopy. As was observed for phenylpyrrole, the unsaturted rings of PBN become collectively more planar following excitation with UV light, in support of the planar ICT model. However, in PDBN the twist/inversion angle between rings is nearly zero in both the ground and excited electronic states. The unperturbed dipole moments measured here, taken in conjunction with available solvatochromism data, provide an estimate for the polarization, dispersion, and charge transfer contributions to solvent-mediated excited state stabilization. J.A. Thomas, J.W. Young, A.J. Fleisher, L. Álvarez-Valtierra, and D.W. Pratt, J. Phys. Chem. Lett. 1, 2017 (2010).

  5. Infrared spectroscopy of narrow gap donor-acceptor polymer-based ambipolar transistors

    NASA Astrophysics Data System (ADS)

    Khatib, Omar; Yuen, Jonathan; Wilson, Jim; Kumar, Rajeev; di Ventra, Massimiliano; Heeger, Alan; Basov, Dimitri

    2013-03-01

    Donor-acceptor (D-A) copolymers have recently emerged as versatile materials for use in a large variety of device applications. Specifically, these systems possess extremely narrow band gaps, enabling ambipolar charge transport when integrated in solution-processed organic field-effect transistors (OFETs). However, the fundamentals of electronic transport in this class of materials remain unexplored. We present a systematic investigation of ambipolar charge injection in a family of narrow-gap D-A conjugated polymers based on benzobisthiadiazole (BBT) using infrared (IR) spectroscopy. We observe a significant modification of the absorption edge in polymer-based OFETs under the applied electric field. The absorption edge reveals hardening under electron injection and softening under hole injection. Additionally, we register localized vibrational resonances associated with injected charges. Our findings indicate a significant self-doping of holes that is modified by charge injection. Observations of both electron and hole transport with relatively high carrier mobility strongly suggest an inhomogeneous, phase-separated conducting polymer.

  6. Part I. The fire properties of polymer clay nanocomposites. Part II. Thermal rearrangement of donor-acceptor substituted cyclopropanes

    NASA Astrophysics Data System (ADS)

    Su, Shengpei

    2003-08-01

    This work consists of two parts. Part I, which includes chapter 1--5, is focused on the fire properties of nanocomposites while part II deals with thermal rearrangement of the donor-acceptor cyclopropanes. In chapter 1 of the first part an introduction to the preparation of polymer-clay nanocomposites is provided along with their application to fire retardancy. Chapter 2 details the exfoliation process of clay using in situ polymerization; the results show that the exfoliation process is related to the monomer, the modified clay and the initiator. Chapter 3 concentrates on the preparation of nanocomposites by melt blending with polymer modified clays. Three different polymer modified clays (PS, PMMA and PBD modified clay) and six polymers (PS, HIPS, ABS, PMMA, PP and PE) are reported. The morphology, thermal stability, fire behavior and mechanical properties were studied. This research shows that the exfoliation process by melt blending is controlled by the types of interactions between the various polymers, the silicate surfaces and the organic modifier. The combination of polar polymer matrix and non-polar polymer modified clay with large d-spacing will be more likely to give the exfoliated nanocomposites. TGA-FTIR results show that the mechanism of degradation of polystyrene is changed in the presence of the clay. In order to better understand the effects of the organic modifier, PS surfactants with five different pendant groups, dimethylhexadecylamine, trimethylamine, dimethylbenzylamine, 1,2-dimethylimidizole and triphenylphosphine, were used and the results show that the degradation depends upon the pendant. Chapter 5 provides some suggestions for future work based upon this work. The synthesis of several new and previously reported donor-acceptor cyclopropanes is reported in part II. The study shows that the facility of the donor-acceptor cyclopropane ring cleavage is strongly influenced by the kind of activating substitutes on the cyclopropane ring, and the

  7. Photophysics and charge transfer in donor-acceptor triblock copolymer photovoltaic materials

    NASA Astrophysics Data System (ADS)

    Schwarz, Kyra N.; Jones, David J.; Smith, Trevor A.; Ghiggino, Kenneth P.

    2014-10-01

    Efficient conversion of solar energy to electricity in low-cost organic photovoltaic (OPV) devices requires the complex interplay between multiple processes and components over various length and time scales. Optimizing device morphology to ensure efficient exciton diffusion and charge transport as well as ensuring efficient charge photogeneration is necessary to achieve optimum performance in new materials. The conjugated polymer electron donor PFM (poly(9,9-diocetyluorene-co-bis-N,N-(4-methylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine)) and electron acceptor F8BT (poly[(9,9-di-n-octyluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)), comprise the novel triblock copolymer PFM-F8BT-PFM. This copolymer is designed to phase separate on the 20-30 nm scale, a domain size ideal for maximizing exciton collection at the donor-acceptor interface. Using steady-state and ultrafast spectroscopic characterization including high repetition rate transient absorption spectroscopy, the dynamics of charge and energy transfer of the component polymers and the triblock co-polymer have been investigated. The results demonstrate that for the homopolymers solvent dependent exciton transport processes dominate, while in the triblock copolymer solutions transient spectroscopy provides evidence for interfacial charge separation.

  8. Giant spatially-resolved self-assembled donor-acceptor molecular heterojunctions

    NASA Astrophysics Data System (ADS)

    Guest, Jeffrey R.; Smerdon, Joseph A.; Giebink, Noel C.; Guisinger, Nathan P.; Darancet, Pierre

    Despite theoretical models predicting that rectification ratios (RR) >1000 should be achievable in molecular rectifiers, demonstrations of this have been rare. It has also been extremely challenging to unravel the structure-function relationships on the nanometer length scales that determine their behavior. Using scanning tunneling microscopy (STM) and spectroscopy (STS), we show that RRs >1000 at biases <500 mV are realized in the two-molecule limit for self-assembled donor-acceptor bilayers of pentacene on C60 on Cu. We show that the system behaves as a molecular analog to a Schottky diode due to strong electronic coupling of C60 to the metallic substrate, and electronic transport is dominated by sequential tunneling from semiconducting pentacene to metallic C60. Furthermore, we demonstrate the extreme sensitivity of the low-bias I (V) characteristics to the molecularly-resolved structure of the heterojunction (HJ), which leads to negative differential resistance and ~ 100 × variation in the rectification ratio within 2 nm of the edge of the molecular HJ. Support was provided by the Department of Energy Office of Basic Energy Sciences (SISGR Grant DE-FG02-09ER16109).

  9. A systematic study of thermochromic aromatic donor-acceptor materials.

    PubMed

    Alvey, Paul M; Reczek, Joseph J; Lynch, Vincent; Iverson, Brent L

    2010-11-19

    Molar mixtures (1:1) of electron-rich dialkoxynapthalene (Dan) and electron-deficient 1,4,5,8-napthalenetetracarboxylic diimide (Ndi) derivatives form highly tunable, columnar mesophases with a dark red color due to a charge transfer absorbance derived from alternating face-centered stacking. Certain Dan-Ndi mixtures undergo a dramatic color change from dark red to an almost colorless material upon crystallizing from the mesophase. Macroscopic morphology of the solid is not changed during this process. In order to investigate the origins of this interesting thermochromic behavior, Dan and Ndi side chains were systematically altered and their 1:1 mixtures were studied. We have previously speculated that the presence or absence of steric interactions due to side chain branching on the aromatic units controlled the level of color change associated with crystallization. Results from the present study further refine this conclusion including a key crystal structure that provides a structural rationale for the observed results. PMID:20973470

  10. A Systematic Study of Thermochromic Aromatic Donor-Acceptor Materials

    PubMed Central

    Alvey, Paul M.; Reczek, Joseph J.; Lynch, Vincent; Iverson, Brent L.

    2010-01-01

    1:1 molar mixtures of electron rich dialkoxynapthalene (Dan) and electron deficient 1,4,5,8-napthalenetetracarboxylic diimide (Ndi) derivatives form highly tunable, columnar mesophases with a dark red color due to a charge transfer absorbance derived from alternating face-centered stacking. Certain Dan-Ndi mixtures undergo a dramatic color change from dark red to an almost colorless material upon crystallizing from the mesophase. Macroscopic morphology of the solid is not changed during this process. In order to investigate the origins of this interesting thermochromic behavior, Dan and Ndi side chains were systematically altered and their 1:1 mixtures studied. We have previously speculated that the presence or absence of steric interactions due to side chain branching on the aromatic units controlled the level of color change associated with crystallization. Results from the present study further refine this conclusion including a key crystal structure that provides a structural rationale for the observed results. PMID:20973470

  11. Photophysical Properties and Efficient, Stable, Electrogenerated Chemiluminescence of Donor-Acceptor Molecules Exhibiting Thermal Spin Upconversion.

    PubMed

    Ishimatsu, Ryoichi; Edura, Tomohiko; Adachi, Chihaya; Nakano, Koji; Imato, Toshihiko

    2016-03-24

    The photophysical properties and electrogenerated chemiluminescence (ECL) of three donor-acceptor molecules composed of dicyanobenzene and methyl-, tert-butyl-, and phenyl-substituted carbazolyl groups, 1,2,3,5-tetrakis(3,6-disubstituted-carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN-Me, 4CzIPN-tBu, and 4CzIPN-Ph, respectively) are described. These molecules show delayed fluorescence as a result of thermal spin upconversion from the lowest triplet state to the lowest singlet state at room temperature. The three molecules showed yellow to yellowish-red ECL. Remarkably, the ECL efficiencies of 4CzIPN-tBu in dichloromethane reached almost 40 %. Moreover, stable ECL was emitted from 4CzIPN-tBu and 4CzIPN-Ph. In case of 4CzIPN-Me, the ECL intensity decreased during voltage cycles because of polymerization. Quantum chemical calculations revealed that polymerization was inhibited by the steric hindrance of the bulky tert-butyl and phenyl groups on the carbazolyl moieties and lowered the spin density on the carbazolyl groups through electron conjugation for 4CzIPN-Ph. PMID:26916843

  12. Design of Bicontinuous Donor/Acceptor Morphologies for Use as Organic Solar Cell Active Layers

    NASA Astrophysics Data System (ADS)

    Kipp, Dylan; Mok, Jorge; Verduzco, Rafael; Ganesan, Venkat

    Two of the primary challenges limiting the marketability of organic solar cells are i) the smaller device efficiency of the organic solar cell relative to the conventional silicon-based solar cell and ii) the long term thermal instability of the device active layer. The achievement of equilibrium donor/acceptor morphologies with the characteristics believed to yield high device performance characteristics could address each of these two challenges. In this work, we present the results of a combined simulations and experiments-based approach to investigate if a conjugated BCP additive can be used to control the self-assembled morphologies taken on by conjugated polymer/PCBM mixtures. First, we use single chain in mean field Monte Carlo simulations to identify regions within the conjugated polymer/PCBM composition space in which addition of copolymers can lead to bicontinuous equilibrium morphologies with high interfacial areas and nanoscale dimensions. Second, we conduct experiments as directed by the simulations to achieve such morphologies in the PTB7 + PTB7- b-PNDI + PCBM model blend. We characterize the results of our experiments via a combination of transmission electron microscopy and X-ray scattering techniques and demonstrate that the morphologies from experiments agree with those predicted in simulations. Accordingly, these results indicate that the approach utilized represents a promising approach to intelligently design the morphologies taken on by organic solar cell active layers.

  13. Ab-initio study of donor-acceptor codoping for n-type CuO

    SciTech Connect

    Peng, Yuan; Wang, Junling; Zheng, Jianwei; Wu, Ping

    2014-10-28

    Single n-type dopant in CuO has either a deep donor level or limited solubility, inefficient in generating free electrons. We have performed ab-initio study of the donor-acceptor codoping to obtain n-type CuO. Our results show that N codoping can slightly improve the donor level of Zr and In by forming shallower n-type complexes (Zr{sub Cu}-N{sub O} and 2In{sub Cu}-N{sub O}), but their formation energies are too high to be realized in experiments. However, Li codoping with Al and Ga is found to be relatively easy to achieve. 2Al{sub Cu}-Li{sub Cu} and 2Ga{sub Cu}-Li{sub Cu} have shallower donor levels than single Al and Ga by 0.14 eV and 0.08 eV, respectively, and their formation energies are reasonably low to act as efficient codopants. Moreover, Li codoping with both Al and Ga produce an empty impurity band just below the host conduction band minimum, which may reduce the donor ionization energy at high codoping concentrations.

  14. A charge carrier transport model for donor-acceptor blend layers

    NASA Astrophysics Data System (ADS)

    Fischer, Janine; Widmer, Johannes; Kleemann, Hans; Tress, Wolfgang; Koerner, Christian; Riede, Moritz; Vandewal, Koen; Leo, Karl

    2015-01-01

    Highly efficient organic solar cells typically comprise donor-acceptor blend layers facilitating effective splitting of excitons. However, the charge carrier mobility in the blends can be substantially smaller than in neat materials, hampering the device performance. Currently, available mobility models do not describe the transport in blend layers entirely. Here, we investigate hole transport in a model blend system consisting of the small molecule donor zinc phthalocyanine (ZnPc) and the acceptor fullerene C60 in different mixing ratios. The blend layer is sandwiched between p-doped organic injection layers, which prevent minority charge carrier injection and enable exploiting diffusion currents for the characterization of exponential tail states from a thickness variation of the blend layer using numerical drift-diffusion simulations. Trap-assisted recombination must be considered to correctly model the conductivity behavior of the devices, which are influenced by local electron currents in the active layer, even though the active layer is sandwiched in between p-doped contacts. We find that the density of deep tail states is largest in the devices with 1:1 mixing ratio (Et = 0.14 eV, Nt = 1.2 × 1018 cm-3) directing towards lattice disorder as the transport limiting process. A combined field and charge carrier density dependent mobility model are developed for this blend layer.

  15. A charge carrier transport model for donor-acceptor blend layers

    SciTech Connect

    Fischer, Janine Widmer, Johannes; Koerner, Christian; Vandewal, Koen; Leo, Karl; Kleemann, Hans; Tress, Wolfgang; Riede, Moritz

    2015-01-28

    Highly efficient organic solar cells typically comprise donor-acceptor blend layers facilitating effective splitting of excitons. However, the charge carrier mobility in the blends can be substantially smaller than in neat materials, hampering the device performance. Currently, available mobility models do not describe the transport in blend layers entirely. Here, we investigate hole transport in a model blend system consisting of the small molecule donor zinc phthalocyanine (ZnPc) and the acceptor fullerene C{sub 60} in different mixing ratios. The blend layer is sandwiched between p-doped organic injection layers, which prevent minority charge carrier injection and enable exploiting diffusion currents for the characterization of exponential tail states from a thickness variation of the blend layer using numerical drift-diffusion simulations. Trap-assisted recombination must be considered to correctly model the conductivity behavior of the devices, which are influenced by local electron currents in the active layer, even though the active layer is sandwiched in between p-doped contacts. We find that the density of deep tail states is largest in the devices with 1:1 mixing ratio (E{sub t} = 0.14 eV, N{sub t} = 1.2 × 10{sup 18 }cm{sup −3}) directing towards lattice disorder as the transport limiting process. A combined field and charge carrier density dependent mobility model are developed for this blend layer.

  16. Controlling charge separation and recombination by chemical design in donor-acceptor dyads.

    PubMed

    Liu, Li; Eisenbrandt, Pierre; Roland, Thomas; Polkehn, Matthias; Schwartz, Pierre-Olivier; Bruchlos, Kirsten; Omiecienski, Beatrice; Ludwigs, Sabine; Leclerc, Nicolas; Zaborova, Elena; Léonard, Jérémie; Méry, Stéphane; Burghardt, Irene; Haacke, Stefan

    2016-07-21

    Conjugated donor-acceptor block co-oligomers that self-organize into D-A mesomorphic arrays have raised increasing interest due to their potential applications in organic solar cells. We report here a combined experimental and computational study of charge transfer (CT) state formation and recombination in isolated donor-spacer-acceptor oligomers based on bisthiophene-fluorene (D) and perylene diimide (A), which have recently shown to self-organize to give a mesomorphic lamellar structure at room temperature. Using femtosecond transient absorption spectroscopy and Time-Dependent Density Functional Theory in combination with the Marcus-Jortner formalism, the observed increase of the CT lifetimes is rationalized in terms of a reduced electronic coupling between D and A brought about by the chemical design of the donor moiety. A marked dependence of the CT lifetime on solvent polarity is observed, underscoring the importance of electrostatic effects and those of the environment at large. The present investigation therefore calls for a more comprehensive design approach including the effects of molecular packing. PMID:27341086

  17. Benzo[c][1,2,5]thiadiazole Donor-Acceptor Dyes: A Synthetic, Spectroscopic, and Computational Study.

    PubMed

    Barnsley, Jonathan E; Shillito, Georgina E; Larsen, Christopher B; van der Salm, Holly; Wang, Lei E; Lucas, Nigel T; Gordon, Keith C

    2016-03-24

    The synthesis, optical characterization and computational modeling of seven benzo[c][1,2,5]thiadiazole (BTD) donor-acceptor dyes are reported. These dyes have been studied using electrochemical analysis, electronic absorption, emission, and Raman and resonance Raman spectroscopies coupled with various density functional theoretical approaches. Crystal structure geometries on a number of these compounds are also reported. The optical spectra are dominated by low energy charge-transfer states; this may be modulated by the coupling between donor and acceptor through variation in donor energy, variation of the donor-acceptor torsion angle, and incorporation of an insulating bridge. These modifications result in a perturbation of the excitation energy for this charge-transfer transition of up to ∼2000 cm(-1). Emission spectra exhibit significant solvatochromisim, with Lippert-Mataga analysis yielding Δμ between 8 and 33 D. Predicted λmax, ε, and Raman cross sections calculated by M06L, B3LYP, PBE0, M06, CAM-B3LYP, and ωB97XD DFT functionals were compared to experimental results and analyzed using multivariate analysis, which shows that hybrid functionals with 20-27% HF best predict ground state absorption, while long-range corrected functionals best predict molecular polarizabilities. PMID:26918584

  18. High-resolution noncontact AFM and Kelvin probe force microscopy investigations of self-assembled photovoltaic donor-acceptor dyads.

    PubMed

    Grévin, Benjamin; Schwartz, Pierre-Olivier; Biniek, Laure; Brinkmann, Martin; Leclerc, Nicolas; Zaborova, Elena; Méry, Stéphane

    2016-01-01

    Self-assembled donor-acceptor dyads are used as model nanostructured heterojunctions for local investigations by noncontact atomic force microscopy (nc-AFM) and Kelvin probe force microscopy (KPFM). With the aim to probe the photo-induced charge carrier generation, thin films deposited on transparent indium tin oxide substrates are investigated in dark conditions and upon illumination. The topographic and contact potential difference (CPD) images taken under dark conditions are analysed in view of the results of complementary transmission electron microscopy (TEM) experiments. After in situ annealing, it is shown that the dyads with longer donor blocks essentially lead to standing acceptor-donor lamellae, where the acceptor and donor groups are π-stacked in an edge-on configuration. The existence of strong CPD and surface photo-voltage (SPV) contrasts shows that structural variations occur within the bulk of the edge-on stacks. SPV images with a very high lateral resolution are achieved, which allows for the resolution of local photo-charging contrasts at the scale of single edge-on lamella. This work paves the way for local investigations of the optoelectronic properties of donor-acceptor supramolecular architectures down to the elementary building block level. PMID:27335768

  19. Dynamics of exciton dissociation in donor-acceptor polymer heterojunctions.

    PubMed

    Sun, Zhen; Stafström, Sven

    2013-04-28

    Exciton dissociation in a donor-accepter polymer heterojunction has been simulated using a nonadiabatic molecular dynamics approach, which allows for the coupled evolution of the nuclear degrees of freedom and the electronic degrees of freedom described by multiconfigurational electronic wavefunctions. The simulations reveal important details of the charge separation process: the exciton in the donor polymer first dissociates into a "hot" charge transfer state, which is best described as a polaron pair. The polaron pair can be separated into free polaron charge carriers if a sufficiently strong external electric field is applied. We have also studied the effects of inter-chain interaction, temperature, and the external electric field strength. Increasing inter-chain interactions makes it easier for the exciton to dissociate into a polaron pair state, but more difficult for the polaron pair to dissociate into free charge carriers. Higher temperature and higher electric field strength both favor exciton dissociation as well as the formation of free charge carriers. PMID:23635169

  20. Acceptor-donor-acceptor-based small molecules with varied crystallinity: processing additive-induced nanofibril in blend film for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Li, Chao; Chen, Yujin; Zhao, Yue; Wang, Huifang; Zhang, Wei; Li, Yaowen; Yang, Xiaoming; Ma, Changqi; Chen, Liwei; Zhu, Xiulin; Tu, Yingfeng

    2013-09-01

    A series of acceptor-donor-acceptor-based small molecules (SMs) with varied crystallinity were successfully synthesized. The processing additive can induce the SMs to self-organize as nanofibrils with higher crystallinity and controlled scales of nanofibrils, which have significant influence on the photovoltaic performance.A series of acceptor-donor-acceptor-based small molecules (SMs) with varied crystallinity were successfully synthesized. The processing additive can induce the SMs to self-organize as nanofibrils with higher crystallinity and controlled scales of nanofibrils, which have significant influence on the photovoltaic performance. Electronic supplementary information (ESI) available: Synthetic process and characterizations of SMs; TGA, electrochemical properties, molecular orbital surfaces of SMs; AFM images of SM:PC71BM blend films; EQE curves; optical, electrochemical properties and photovoltaic parameters. See DOI: 10.1039/c3nr03048b

  1. Digital memory versatility of fully π-conjugated donor-acceptor hybrid polymers.

    PubMed

    Ko, Yong-Gi; Kim, Dong Min; Kim, Kyungtae; Jung, Sungmin; Wi, Dongwoo; Michinobu, Tsuyoshi; Ree, Moonhor

    2014-06-11

    The fully π-conjugated donor-acceptor hybrid polymers Fl-TPA, Fl-TPA-TCNE, and Fl-TPA-TCNQ, which are composed of fluorene (Fl), triphenylamine (TPA), dimethylphenylamine, alkyne, alkyne-tetracyanoethylene (TCNE) adduct, and alkyne-7,7,8,8-tetracyanoquinodimethane (TCNQ) adduct, were synthesized. These polymers are completely amorphous in the solid film state and thermally stable up to 291-409 °C. Their molecular orbital levels and band gaps vary with their compositions. The TCNE and TCNQ units, despite their electron-acceptor characteristics, were found to enhance the π-conjugation lengths of Fl-TPA-TCNE and Fl-TPA-TCNQ (i.e., to produce red shifts in their absorption spectra and significant reductions in their band gaps). These changes are reflected in the electrical digital memory behavior of the polymers. Moreover, the TCNE and TCNQ units were found to diversify the digital memory modes and to widen the active polymer layer thickness window. In devices with aluminum top and bottom electrodes, the Fl-TPA polymer exhibits stable unipolar permanent memory behavior with high reliability. The Fl-TPA-TCNE and Fl-TPA-TCNQ devices exhibit stable unipolar permanent memory behavior as well as dynamic random access memory behavior with excellent reliability. These polymer devices were found to operate by either hole injection or hole injection along with electron injection, depending on the polymer composition. Overall, this study demonstrated that the incorporation of π-conjugated cyano moieties, which control both the π-conjugation length and electron-accepting power, is a sound approach for the design and synthesis of high-performance digital memory polymers. The TCNE and TCNQ polymers synthesized in this study are highly suitable active materials for the low-cost mass production of high-performance, polarity-free, programmable, volatile, and permanent memory devices that can be operated with very low power consumption, high ON/OFF current ratios, and high

  2. Theoretical estimation of the rate of photoinduced charge transfer reactions in triphenylamine C60 donor-acceptor conjugate.

    PubMed

    Martínez, Juan Pablo; Solà, Miquel; Voityuk, Alexander A

    2016-06-01

    Fullerene-based molecular heterojunctions such as the [6,6]-pyrrolidine-C60 donor-acceptor conjugate containing triphenylamine (TPA) are potential materials for high-efficient dye-sensitized solar cells. In this work, we estimate the rate constants for the photoinduced charge separation and charge recombination processes in TPA-C60 using the unrestricted and time-dependent DFT methods. Different schemes are applied to evaluate excited state properties and electron transfer parameters (reorganization energies, electronic couplings, and Gibbs energies). The use of open-shell singlet or triplet states, several density functionals, and continuum solvation models is discussed. Strengths and limitations of the computational approaches are highlighted. The present benchmark study provides an overview of the expected performance of DFT-based methodologies in the description of photoinduced charge transfer reactions in fullerene heterojunctions. © 2016 Wiley Periodicals, Inc. PMID:26992355

  3. Exciton dissociation at organic small molecule donor-acceptor interfaces (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Robey, Steven W.

    2015-08-01

    Exciton dissociation at organic semiconductor donor-acceptor (D-A) heterojunctions is critical for the performance of organic photovoltaic (OPV) structures. Interfacial charge separation and recombination processes control device efficiency. We have investigated these fundamental interfacial issues using time-resolved two-photon photoemission (TR-2PPE), coupled with the formation of well-controlled D-A structures by organic molecular beam epitaxy. The interfacial electronic and molecular structure of these model interfaces was well-characterized using scanning tunneling microscopy and ultraviolet photoemission. Exciton dissociation dynamics were investigated by using a sub-picosecond pump pulse to create Pc π-->π* transitions, producing a population of singlet (S1) Pc excitons. The subsequent decay dynamics of this population was monitored via photoemission with a time-delayed UV pulse. For CuPcC60 interfaces, S1 exciton population decay in the interfacial CuPc layer was much faster than decay in the bulk due to interfacial charge separation. The rate constant for exciton dissociation was found to be ≍ 7 x 10 12 sec-1 (≍ 140 fs). Excitons that lose energy via intersystem crossing (ISC) to triplet levels dissociate approximately 500 to 1000 times slower. The dependence of exciton dissociation on separation was also studied. Exciton dissociation falls of rapidly with distance from the interface. Dissociation from the 2nd, and subsequent, layers of H2Pc is reduced by at least a factor of 10 from that in the interfacial layer. Finally, investigations of the relative efficiency for interfacial exciton dissociation by alternative acceptors based on perylene cores, (perylene tetracarboxylic dianhydride, or PTCDA) compared to fullerene-based acceptors such as C60 will also be discussed.

  4. Optical properties of disilane-bridged donor-acceptor architectures: strong effect of substituents on fluorescence and nonlinear optical properties.

    PubMed

    Shimada, Masaki; Yamanoi, Yoshinori; Matsushita, Tomonori; Kondo, Takashi; Nishibori, Eiji; Hatakeyama, Akari; Sugimoto, Kunihisa; Nishihara, Hiroshi

    2015-01-28

    A series of disilane-bridged donor-acceptor architectures 1-9 containing strong electron-donating and -withdrawing substituents were designed and synthesized in acceptable yields. The substituents substantially affected the fluorescence and nonlinear optical properties of the compounds. In the solid state, the compounds showed purple-blue fluorescence (λ(em) = 360-420 nm) with high quantum yields (up to 0.81). Compound 3, which had p-N,N-dimethylamino and o-cyano substituents, exhibited optical second harmonic generation (activity 2.9 times that of urea, calculated molecular hyperpolarizability β = 1.6 × 10(-30) esu) in the powder state. Density functional theory calculations for the ground and excited states indicated that both the locally excited state and the intramolecular charge transfer excited state make important contributions to the luminescence behavior. PMID:25565361

  5. Direct Correlation of Charge Transfer Absorption with Molecular Donor:Acceptor Interfacial Area via Photothermal Deflection Spectroscopy.

    PubMed

    Buchaca-Domingo, Ester; Vandewal, Koen; Fei, Zhuping; Watkins, Scott E; Scholes, Fiona H; Bannock, James H; de Mello, John C; Richter, Lee J; DeLongchamp, Dean M; Amassian, Aram; Heeney, Martin; Salleo, Alberto; Stingelin, Natalie

    2015-04-29

    Here we show that the charge transfer (CT) absorption signal in bulk-heterojunction solar cell blends, measured by photothermal deflection spectroscopy, is directly proportional to the density of molecular donor:acceptor interfaces. Since the optical transitions from the ground state to the interfacial CT state are weakly allowed at photon energies below the optical gap of both the donor and acceptor, we can exploit the use of this sensitive linear absorption spectroscopy for such quantification. Moreover, we determine the absolute molar extinction coefficient of the CT transition for an archetypical polymer:fullerene interface. The latter is ∼100 times lower than the extinction coefficient of the donor chromophore involved, allowing us to experimentally estimate the transition dipole moment as 0.3 D and the electronic coupling between the ground and CT states to be on the order of 30 meV. PMID:25856143

  6. Photoinduced Charge Transfer and Electrochemical Properties of Triphenylamine Ih-Sc3N@C80 Donor-Acceptor Conjugates

    PubMed Central

    Pinzón, Julio R.; Gasca, Diana C.; Shankara, Gayathri. S; Bottari, Giovanni; Torres, Tomás; Guldi, Dirk M.; Echegoyen, Luis

    2009-01-01

    Two isomeric [5,6]-pyrrolidine-Ih-Sc3N@C80 electron donor acceptor conjugates containing triphenylamine (TPA) as the donor system were synthesized. Electrochemical and photophysical studies of the novel conjugates were made and compared with those of their C60 analogues, in order to determine i) the effect of the linkage position (N-substituted versus 2-substituted pyrrolidine) of the donor system in the formation of photoinduced charge separated states, ii) the thermal stability towards the retro-cycloaddition reaction and iii) the effect of changing C60 for Ih-Sc3N@C80 as the electron acceptor. It was found that when the donor is connected to the pyrrolidine nitrogen atom, the resulting dyad produces a significantly longer lived radical pair than the corresponding 2-substituted isomer for both the C60 and Ih-Sc3N@C80 dyads. In addition to that, the N-substituted TPA-Ih-Sc3N@C80 dyad has much better thermal stability than the 2-subtituted one. Finally, the Ih-Sc3N@C80 dyads have considerably longer lived charge separated states than their C60 analogues, thus approving the advantage of using Ih-Sc3N@C80 instead of C60 as the acceptor for the construction of fullerene based donor acceptor conjugates. These findings are important for the design and future application of Ih-Sc3N@C80 dyads as materials for the construction of plastic organic solar cells. PMID:19445462

  7. Tuning of Stepwise Neutral-Ionic Transitions by Acceptor Site Doping in Alternating Donor/Acceptor Chains.

    PubMed

    Nakabayashi, Keita; Nishio, Masaki; Miyasaka, Hitoshi

    2016-03-01

    The stepwise neutral-ionic (N-I) phase transition found in the alternating donor/acceptor (DA) chain [Ru2(2,3,5,6-F4PhCO2)4(DMDCNQI)]·2(p-xylene) (0; 2,3,5,6-F4PhCO2(-) = 2,3,5,6-tetrafluorobenzoate; DMDCNQI = 2,5-dimethyl-N,N'-dicyanoquinonediimine) was tuned by partly substituting the acceptor DMDCNQI with 2,5-dimethoxy-N,N'-dicyanoquinonediimine (DMeODCNQI), which displays a poorer electron affinity in an isostructural series. The site-doped series comprised [Ru2(2,3,5,6-F4PhCO2)4(DMDCNQI)1-x(DMeODCNQI)x]·2(p-xylene) for doping rates (x) = 0.05 (0.05-MeO), 0.10 (0.10-MeO), 0.15 (0.15-MeO), and 0.20 (0.20-MeO). The neutral chain [Ru2(2,3,5,6-F4PhCO2)4(DMeODCNQI)]·4(p-xylene) (1), which only contained DMeODCNQI, was also characterized. All site-doped compounds were isostructural to 0 except 1 despite their identical DA chain motif. Except at an x value of 0.20, they displayed a two-step N-I transition involving an intermediate phase. This transition occurred at high temperatures in 0 but shifted to lower temperatures in a parallel manner with increasing doping rate. Simultaneously, each transition broadened with increasing doping rate, leading to a convergence of two transitions at an x value approximating 0.2. Donor/acceptor-site-doping techniques present somewhat different impacts in terms of interchain Coulomb effects. PMID:26878151

  8. Photoconductive and supramolecularly engineered organic field-effect transistors based on fibres from donor-acceptor dyads

    NASA Astrophysics Data System (ADS)

    Treier, Matthias; Liscio, Andrea; Mativetsky, Jeffrey M.; Kastler, Marcel; Müllen, Klaus; Palermo, Vincenzo; Samorì, Paolo

    2012-02-01

    We report on the formation of photoconductive self-assembled fibres by solvent induced precipitation of a HBC-PMI donor-acceptor dyad. Kelvin Probe Force Microscopy revealed that upon illumination with white light the surface potential of the fibres shifted to negative values due to a build-up of negative charge. When integrated in a field-effect transistor (FET) configuration, the devices can be turned `on' much more efficiently using light than conventional bias triggered field-effect, suggesting that these structures could be used for the fabrication of light sensing devices. Such a double gating represents an important step towards bi-functional organic FETs, in which the current through the junction can be modulated both optically (by photoexcitation) and electrically (by gate control).We report on the formation of photoconductive self-assembled fibres by solvent induced precipitation of a HBC-PMI donor-acceptor dyad. Kelvin Probe Force Microscopy revealed that upon illumination with white light the surface potential of the fibres shifted to negative values due to a build-up of negative charge. When integrated in a field-effect transistor (FET) configuration, the devices can be turned `on' much more efficiently using light than conventional bias triggered field-effect, suggesting that these structures could be used for the fabrication of light sensing devices. Such a double gating represents an important step towards bi-functional organic FETs, in which the current through the junction can be modulated both optically (by photoexcitation) and electrically (by gate control). Electronic supplementary information (ESI) available: Experimental details and photoresponse on spin-coated film (3 pages). See DOI: 10.1039/c2nr11635a

  9. Ultrafast Energy Transfer in Ultrathin Organic Donor/Acceptor Blend

    PubMed Central

    Kandada, Ajay Ram Srimath; Grancini, Giulia; Petrozza, Annamaria; Perissinotto, Stefano; Fazzi, Daniele; Raavi, Sai Santosh Kumar; Lanzani, Guglielmo

    2013-01-01

    It is common knowledge that poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend, a prototype system for bulk heterojunction (BHJ) solar cells, consists of a network of tens of nanometers-large donor-rich and acceptor-rich phases separated by extended finely intermixed border regions where PCBM diffuse into P3HT. Here we specifically address the photo-induced dynamics in a 10 nm thin P3HT/PCBM blend that consists of the intermixed region only. Using the multi-pass transient absorption technique (TrAMP) that enables us to perform ultra high sensitive measurements, we find that the primary process upon photoexcitation is ultrafast energy transfer from P3HT to PCBM. The expected charge separation due to hole transfer from PCBM to P3HT occurs in the 100 ps timescale. The derived picture is much different from the accepted view of ultra-fast electron transfer at the polymer/PCBM interface and provides new directions for the development of efficient devices. PMID:23797845

  10. Ultrafast Energy Transfer in Ultrathin Organic Donor/Acceptor Blend

    NASA Astrophysics Data System (ADS)

    Kandada, Ajay Ram Srimath; Grancini, Giulia; Petrozza, Annamaria; Perissinotto, Stefano; Fazzi, Daniele; Raavi, Sai Santosh Kumar; Lanzani, Guglielmo

    2013-06-01

    It is common knowledge that poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend, a prototype system for bulk heterojunction (BHJ) solar cells, consists of a network of tens of nanometers-large donor-rich and acceptor-rich phases separated by extended finely intermixed border regions where PCBM diffuse into P3HT. Here we specifically address the photo-induced dynamics in a 10 nm thin P3HT/PCBM blend that consists of the intermixed region only. Using the multi-pass transient absorption technique (TrAMP) that enables us to perform ultra high sensitive measurements, we find that the primary process upon photoexcitation is ultrafast energy transfer from P3HT to PCBM. The expected charge separation due to hole transfer from PCBM to P3HT occurs in the 100 ps timescale. The derived picture is much different from the accepted view of ultra-fast electron transfer at the polymer/PCBM interface and provides new directions for the development of efficient devices.

  11. Seeded on-surface supramolecular growth for large area conductive donor-acceptor assembly.

    PubMed

    Goudappagouda; Chithiravel, Sundaresan; Krishnamoorthy, Kothandam; Gosavi, Suresh W; Babu, Sukumaran Santhosh

    2015-07-01

    Charge transport features of organic semiconductor assemblies are of paramount importance. However, large-area extended supramolecular structures of donor-acceptor combinations with controlled self-assembly pathways are hardly accessible. In this context, as a representative example, seeded on-surface supramolecular growth of tetrathiafulvalene and tetracyano-p-quinodimethane (TTF-TCNQ) using active termini of solution-formed sheaves has been introduced to form an extended assembly. We demonstrate for the first time, the creation of a large-area donor-acceptor assembly on the surface, which is practically very tedious, using a seeded, evaporation-assisted growth process. The excellent molecular ordering in this assembly is substantiated by its good electrical conductivity (~10⁻² S cm⁻¹). The on-surface assembly via both internally formed and externally added sheaf-like seeds open new pathways in supramolecular chemistry and device applications. PMID:26036616

  12. Alteration of the Donor/Acceptor Spectrum of the (S)-Amine Transaminase from Vibrio fluvialis.

    PubMed

    Genz, Maika; Vickers, Clare; van den Bergh, Tom; Joosten, Henk-Jan; Dörr, Mark; Höhne, Matthias; Bornscheuer, Uwe T

    2015-01-01

    To alter the amine donor/acceptor spectrum of an (S)-selective amine transaminase (ATA), a library based on the Vibrio fluvialis ATA targeting four residues close to the active site (L56, W57, R415 and L417) was created. A 3DM-derived alignment comprising fold class I pyridoxal-5'-phosphate (PLP)-dependent enzymes allowed identification of positions, which were assumed to determine substrate specificity. These positions were targeted for mutagenesis with a focused alphabet of hydrophobic amino acids to convert an amine:α-keto acid transferase into an amine:aldehyde transferase. Screening of 1200 variants revealed three hits, which showed a shifted amine donor/acceptor spectrum towards aliphatic aldehydes (mainly pentanal), as well as an altered pH profile. Interestingly, all three hits, although found independently, contained the same mutation R415L and additional W57F and L417V substitutions. PMID:26569229

  13. Donor-Acceptor Heterojunction Configurations Based on DNA-Multichromophore Arrays.

    PubMed

    Nakamura, Mitsunobu; Tsuto, Koji; Jomura, Ayumi; Takada, Tadao; Yamana, Kazushige

    2015-08-10

    Multichromophore arrays of bis(2-thienyl)diketopyrrolopyrrole (DPP) and naphthalenediimide (NDI) with two Zn(II) -cyclens were constructed using thymidine DNA as a scaffold through the binding of the Zn(II) -cyclens with thymine bases. We demonstrate photocurrent generation in a donor-acceptor heterojunction configuration consisting of the DPP (donor) and NDI (acceptor) arrays co-immobilized on an Au electrode. The co-immobilized electrode exhibited good photocurrent responses because of the efficient charge separation between the DPP and NDI arrays. In contrast, an immobilized electrode consisting of randomly assembled DPP-NDI arrays generated no photocurrent response because DPP formed ground-state charge-transfer complexes with NDI in the randomly assembled arrays. Therefore, our approach to generate donor-acceptor heterojunctions based on DNA-multichromophore arrays is a useful method to efficiently generate photocurrent. PMID:26179473

  14. Thermally Activated Delayed Fluorescence Materials Based on Homoconjugation Effect of Donor-Acceptor Triptycenes.

    PubMed

    Kawasumi, Katsuaki; Wu, Tony; Zhu, Tianyu; Chae, Hyun Sik; Van Voorhis, Troy; Baldo, Marc A; Swager, Timothy M

    2015-09-23

    Donor-acceptor triptycences, TPA-QNX(CN)2 and TPA-PRZ(CN)2, were synthesized and their emissive properties were studied. They exhibited a blue-green fluorescence with emission lifetimes on the order of a microsecond in cyclohexane at room temperature. The long lifetime emission is quenched by O2 and is attributed to thermally activated delayed florescence (TADF). Unimolecular TADF is made possible by the separation and weak coupling due to homoconjugation of the HOMO and LUMO on different arms of the three-dimensional donor-acceptor triptycene. Organic light emitting devices (OLEDs) were fabricated using TPA-QNX(CN)2 and TPA-PRZ(CN)2 as emitters which displayed electroluminescence with efficiencies as high as 9.4% EQE. PMID:26367852

  15. Alteration of the Donor/Acceptor Spectrum of the (S)-Amine Transaminase from Vibrio fluvialis

    PubMed Central

    Genz, Maika; Vickers, Clare; van den Bergh, Tom; Joosten, Henk-Jan; Dörr, Mark; Höhne, Matthias; Bornscheuer, Uwe T.

    2015-01-01

    To alter the amine donor/acceptor spectrum of an (S)-selective amine transaminase (ATA), a library based on the Vibrio fluvialis ATA targeting four residues close to the active site (L56, W57, R415 and L417) was created. A 3DM-derived alignment comprising fold class I pyridoxal-5′-phosphate (PLP)-dependent enzymes allowed identification of positions, which were assumed to determine substrate specificity. These positions were targeted for mutagenesis with a focused alphabet of hydrophobic amino acids to convert an amine:α-keto acid transferase into an amine:aldehyde transferase. Screening of 1200 variants revealed three hits, which showed a shifted amine donor/acceptor spectrum towards aliphatic aldehydes (mainly pentanal), as well as an altered pH profile. Interestingly, all three hits, although found independently, contained the same mutation R415L and additional W57F and L417V substitutions. PMID:26569229

  16. Synthesis and mesomorphic behavior of a donor-acceptor-type hexaazatriphenylene.

    PubMed

    Chang, Tsu-Hsin; Wu, Bi-Ru; Chiang, Michael Y; Liao, Su-Chih; Ong, Chi Wi; Hsu, Hsiu-Fu; Lin, Shu-Yu

    2005-09-15

    [structure: see text] A new donor-acceptor, 1,4,5,8,9,12-hexaazatriphenylene HATCNOR(n), is described. The synthesis of HATCNOR1 and HATCNOR6 is achieved by the regioselective displacement of 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile (HATCN) with an alkoxy group. The X-ray analysis revealed self-assembly of HATCNOR1 in the solid state. HATCNOR6 is the new difunctionalized hexaazatriphenylene discotic liquid crystal. PMID:16146355

  17. Molecular assembly of amino acid interlinked, topologically symmetric, π-complementary donor-acceptor-donor triads.

    PubMed

    Avinash, M B; Sandeepa, K V; Govindaraju, T

    2013-01-01

    Amino acid interlinked pyrene and naphthalenediimide (NDI) based novel donor-acceptor-donor (D-A-D) triads are designed to exploit their topological symmetry and complementary π-character for facile charge-transfer complexation. Consequently, free-floating high-aspect-ratio supercoiled nanofibres and hierarchical helical bundles of triads are realized by modulating the chemical functionality of interlinking amino acids. PMID:23946856

  18. Ultra-flexible nonvolatile memory based on donor-acceptor diketopyrrolopyrrole polymer blends

    PubMed Central

    Zhou, Ye; Han, Su-Ting; Yan, Yan; Zhou, Li; Huang, Long-Biao; Zhuang, Jiaqing; Sonar, Prashant; Roy, V. A. L.

    2015-01-01

    Flexible memory cell array based on high mobility donor-acceptor diketopyrrolopyrrole polymer has been demonstrated. The memory cell exhibits low read voltage, high cell-to-cell uniformity and good mechanical flexibility, and has reliable retention and endurance memory performance. The electrical properties of the memory devices are systematically investigated and modeled. Our results suggest that the polymer blends provide an important step towards high-density flexible nonvolatile memory devices. PMID:26029856

  19. Field emission analysis of band bending in donor/acceptor heterojunction

    NASA Astrophysics Data System (ADS)

    Xing, Yingjie; Li, Shuai; Wang, Guiwei; Zhao, Tianjiao; Zhang, Gengmin

    2016-06-01

    The donor/acceptor heterojunction plays an important role in organic solar cells. An investigation of band bending in the donor/acceptor heterojunction is helpful in analysis of the charge transport behavior and for the improvement of the device performance. In this work, we report an approach for detection of band bending in a donor/acceptor heterojunction that has been prepared on a small and sharp tungsten tip. In situ field emission measurements are performed after the deposition process, and a linear Fowler-Nordheim plot is obtained from the fresh organic film surface. The thickness-dependent work function is then measured in the layer-by-layer deposited heterojunction. Several different types of heterojunction (zinc phthalocyanine (ZnPc)/C60, copper phthalocyanine (CuPc)/3,4,9,10-perylenetetracarboxylic bisbenzimidazole, and CuPc/C60) are fabricated and analyzed. The different charge transfer directions in the heterojunctions are distinguished by field emission measurements. The calculation method used to determine the band bending is then discussed in detail. A triple layer heterojunction (C60/ZnPc/CuPc) is also analyzed using this method. A small amount of band bending is measured in the outer CuPc layer. This method provides an independent reference method for determination of the band bending in an organic heterojunction that will complement photoemission spectroscopy and current-voltage measurement methods.

  20. Spectral and intramolecular charge transfer properties in terminal donor/acceptor-substituted all-trans-α,ω-diphenylpolyenes and α,ω-diphenylpolyynes.

    PubMed

    Ma, Xiaonan; Yan, Linyin; Wang, Xuefei; Guo, Qianjin; Xia, Andong

    2011-10-14

    The absorption spectra and intramolecular charge transfer (CT) properties of terminal donor/acceptor-substituted all-trans-α,ω-diphenylpolyenes (DPE) and α,ω-diphenylpolyynes (DPY) molecules with different conjugated bridge length and substitution modes were investigated by using quantum chemical calculations. We calculated the ground state structures and energy of two series of terminal donor/acceptor DPE and DPY by DFT method. The dependence of conjugation length and substitution modes of the electronic absorption spectra was obtained by TDDFT calculation. The hybrid-GGA XC-functional PBE0 employed in this work was selected from several functionals by comparing the calculated electronic spectral data with experimental value. The CIS-based generalized Mulliken-Hush (GMH) approach was further used to calculate coupling values H(AD) of the CT process. The calculation shows that both the HOMO-LUMO energy gaps and average bond length alternations between unsaturated multiple (C≡C and C=C) and saturated single bonds (C-C) decrease regularly with the extension of conjugation. The effective conjugated length (ECL) of DPE and DPY with the same order MM > MP/PM > PP is found together with the regular red shift of the electronic absorption spectra with the extension of conjugation, resulting from the different π-electron delocalization and conjugation efficiency. The GMH analysis further suggests that the CT process in both DPE and DPY is predominated by the through-bond mechanism. The remarkable difference of the conjugated length dependence of squared CT coupling between substituted DPE and DPY is the result of the energetic matching degree of the frontier molecular orbitals between donor/acceptor and the conjugated bridge. PMID:21879052

  1. Cascade Reaction of Donor-Acceptor Cyclopropanes: Mechanistic Studies on Cycloadditions with Nitrosoarenes and cis-Diazenes.

    PubMed

    Chidley, Tristan; Vemula, Naresh; Carson, Cheryl A; Kerr, Michael A; Pagenkopf, Brian L

    2016-06-17

    Tandem ring opening, elimination, and cycloaddition of donor-acceptor cyclopropanes were observed in Yb(OTf)3-catalyzed cycloaddition with nitrosoarenes. The reaction results in formation of tetrahydro-1,2-oxazine instead of the normal cycloadduct isoxazolidine via in situ nitrone formation. A similar cascade sequence was observed with cis-diazines. Mechanistic studies on this unique transformation offer an entirely new approach for reaction design with donor-acceptor cyclopropanes. PMID:27267360

  2. Spectroscopic and dynamical differences between exciplex and electronically excited EDA complex

    NASA Astrophysics Data System (ADS)

    Lim, B. T.; Okajima, S.; Lim, E. C.

    1986-02-01

    We demonstrate here that the electronically excited electron donor-acceptor (EDA) complex can be different from the corresponding exciplex even in the absence of viscosity constraints that prevent the attainment of preferred donor-acceptor orientation.

  3. Density-functional Theory and Beyond for Donor-Acceptor Complexes: The Example of TTF/TCNQ

    NASA Astrophysics Data System (ADS)

    Atalla, Viktor; Yoon, Mina; Scheffler, Matthias

    2012-02-01

    We study the performance of density-functional theory (DFT) with various exchange-correlation (XC) functionals in describing electronic and structural properties of the prototypical donor/acceptor complex TTF/TCNQ. We find that the binding energetics and the amount of electron transfer between TTF and TCNQ depends strongly on the functional. In particular, all semilocal functionals give rise to significant, aritificial electron transfer due to a wrong ordering of Kohn-Sham (KS) levels. We consider the HSE [1] ``family'' of XC functionals using the fraction of exact exchange (α) as adjustable parameter. The optimum XC functional is then identified as that for which the G0W0 quasiparticle correction to the energy gap of the KS LUMO of the acceptor and the HOMO of the donor is minimized. We obtain α˜0.8 which gives an electronic level alignment that is consistent with experiment and free from spurious asymptotic charge transfer. We conclude that the proposed scheme improves the KS spectrum, and that the investigated TTF-TCNQ dimer exhibits intra-molecular electron-density rearrangement rather than electron transfer. [4pt] [1] A.V. Krukau, et al., J. Chem. Phys. 125, 224106 (2006)

  4. A predictive theoretical model for electron tunneling pathways in proteins

    NASA Technical Reports Server (NTRS)

    Onuchic, Jose Nelson; Beratan, David N.

    1990-01-01

    A practical method is presented for calculating the dependence of electron transfer rates on details of the protein medium intervening between donor and acceptor. The method takes proper account of the relative energetics and mutual interactions of the donor, acceptor, and peptide groups. It also provides a quantitative search scheme for determining the important tunneling pathways (specific sequences of localized bonding and antibonding orbitals of the protein which dominate the donor-acceptor electronic coupling) in native and tailored proteins, a tool for designing new proteins with prescribed electron transfer rates, and a consistent description of observed electron transfer rates in existing redox labeled metalloproteins and small molecule model compounds.

  5. Large Spatially Resolved Rectification in a Donor-Acceptor Molecular Heterojunction.

    PubMed

    Smerdon, Joseph A; Giebink, Noel C; Guisinger, Nathan P; Darancet, Pierre; Guest, Jeffrey R

    2016-04-13

    We demonstrate that rectification ratios (RR) of ≳250 (≳1000) at biases of 0.5 V (1.2 V) are achievable at the two-molecule limit for donor-acceptor bilayers of pentacene on C60 on Cu using scanning tunneling spectroscopy and microscopy. Using first-principles calculations, we show that the system behaves as a molecular Schottky diode with a tunneling transport mechanism from semiconducting pentacene to Cu-hybridized metallic C60. Low-bias RRs vary by two orders-of-magnitude at the edge of these molecular heterojunctions due to increased Stark shifts and confinement effects. PMID:26964012

  6. Electronic structure of novel charge transfer compounds: application of Fermi orbital self-interaction corrected density functional theory

    NASA Astrophysics Data System (ADS)

    Hahn, Torsten; Rückerl, Florian; Liebing, Simon; Pederson, Mark

    We present our experimental and theoretical results on novel Picene/F4TCNQ and Manganese-Phthalocyanine/F4TCNQ donor / acceptor systems. We apply the recently developed Fermi-orbital based approach for self-interaction corrected density functional theory (FO-SIC DFT) to these materials and compare the results to standard DFT calculations and to experimental data obtained by photoemission spectroscopy. We focus our analysis on the description of the magnitude of the ground state charge transfer and on the details of the formed hybrid orbitals. Further, we show that for weakly bound donor / acceptor systems the FO-SIC approach delivers a more realistic description of the electronic structure compared to standard DFT calculations Support by DFG FOR1154 is greatly acknowledged.

  7. Molecular Packing Determines Charge Separation in a Liquid Crystalline Bisthiophene-Perylene Diimide Donor-Acceptor Material.

    PubMed

    Polkehn, Matthias; Tamura, Hiroyuki; Eisenbrandt, Pierre; Haacke, Stefan; Méry, Stéphane; Burghardt, Irene

    2016-04-01

    Combined electronic structure and quantum dynamical calculations are employed to investigate charge separation in a novel class of covalently bound bisthiophene-perylene diimide type donor-acceptor (DA) co-oligomer aggregates. In an earlier spectroscopic study of this DA system in a smectic liquid crystalline (LC) film, efficient and ultrafast (subpicosecond) initial charge separation was found to be followed by rapid recombination. By comparison, the same DA system in solution exhibits ultrafast resonant energy transfer followed by slower (picosecond scale) charge separation. The present first-principles study explains these contrasting observations, highlighting the role of an efficient intermolecular charge-transfer pathway that results from the molecular packing in the LC phase. Despite the efficiency of this primary charge-transfer step, long-range charge separation is impeded by a comparatively high Coulomb barrier in conjunction with small electron- and hole-transfer integrals. Quantum dynamical calculations are carried out for a fragment-based model Hamiltonian, parametrized by ab initio second-order Algebraic Diagrammatic Construction (ADC(2)) and Time-Dependent Density Functional Theory (TDDFT) electronic structure calculations. Simulations of coherent vibronic quantum dynamics for up to 156 electronic states and 48 modes are performed using the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method. Excellent agreement with experimentally determined charge separation time scales is obtained, and the spatially coherent nature of the dynamics is analyzed. PMID:26987362

  8. Effect of Oligomer Length on Photophysical Properties of Platinum Acetylide Donor-Acceptor-Donor Oligomers.

    PubMed

    Cekli, Seda; Winkel, Russell W; Schanze, Kirk S

    2016-07-21

    We report a systematic study that explores how the triplet excited state is influenced by conjugation length in a series of benzothiadiazole units containing donor-acceptor-donor (DAD)-type platinum acetylide oligomers and polymer. The singlet and triplet excited states for the series were characterized by an array of photophysical methods including steady-state luminescence spectroscopy and femtosecond-nanosecond transient absorption spectroscopy. In addition to the experimental work, a computational study using density functional theory was conducted to gain more information about the structure, composition, and energies of the frontier molecular orbitals. It is observed that both the singlet and triplet excited states are mainly localized on a single donor-acceptor-donor unit in the oligomers. Interestingly, it is discovered that the intersystem crossing efficiency increases dramatically in the longer oligomers. The effect is attributed to an enhanced contribution of the heavy metal platinum in the frontier orbitals (HOMO and LUMO), an effect that leads to enhanced spin-orbit coupling. PMID:27291712

  9. CVD graphene as interfacial layer to engineer the organic donor-acceptor heterojunction interface properties.

    PubMed

    Zhong, Shu; Zhong, Jian Qiang; Mao, Hong Ying; Wang, Rui; Wang, Yu; Qi, Dong Chen; Loh, Kian Ping; Wee, Andrew Thye Shen; Chen, Zhi Kuan; Chen, Wei

    2012-06-27

    We demonstrate the use of chemical-vapor-deposited (CVD) graphene as an effective indium-tin-oxide (ITO) electrode surface modifier to engineer the organic donor-acceptor heterojunction interface properties in an inverted organic solar cell device configuration. As revealed by in situ near-edge X-ray adsorption fine structure measurement, the organic donor-acceptor heterojunction, comprising copper-hexadecafluoro-phthalocyanine (F16CuPc) and copper phthalocyanine (CuPc), undergoes an obvious orientation transition from a standing configuration (molecular π-plane nearly perpendicular to the substrate surface) on the bare ITO electrode to a less standing configuration with the molecular π-plane stacking adopting a large projection along the direction perpendicular to the electrode surface on the CVD graphene-modified ITO electrode. Such templated less-standing configuration of the organic heterojunction could significantly enhance the efficiency of charge transport along the direction perpendicular to the electrode surface in the planar heterojunction-based devices. Compared with the typical standing organic-organic heterojunction on the bare ITO electrode, our in situ ultraviolet photoelectron spectroscopy experiments reveal that the heterojunction on the CVD graphene modified ITO electrode possesses better aligned energy levels with respective electrodes, hence facilitating effective charge collection. PMID:22662875

  10. Asymmetric intramolecular α-cyclopropanation of aldehydes using a donor/acceptor carbene mimetic.

    PubMed

    Luo, Chaosheng; Wang, Zhen; Huang, Yong

    2015-01-01

    Enantioselective α-alkylation of carbonyl is considered as one of the most important processes for asymmetric synthesis. Common alkylation agents, that is, alkyl halides, are notorious substrates for both Lewis acids and organocatalysts. Recently, olefins emerged as a benign alkylating species via photo/radical mechanisms. However, examples of enantioselective alkylation of aldehydes/ketones are scarce and direct asymmetric dialkylation remains elusive. Here we report an intramolecular α-cyclopropanation reaction of olefinic aldehydes to form chiral cyclopropane aldehydes. We demonstrate that an α-iodo aldehyde can function as a donor/acceptor carbene equivalent, which engages in a formal [2+1] annulation with a tethered double bond. Privileged bicyclo[3.1.0]hexane-type scaffolds are prepared in good optical purity using a chiral amine. The synthetic utility of the products is demonstrated by versatile transformations of the bridgehead formyl functionality. We expect the concept of using α-iodo iminium as a donor/acceptor carbene surrogate will find wide applications in chemical reaction development. PMID:26644194

  11. Asymmetric intramolecular α-cyclopropanation of aldehydes using a donor/acceptor carbene mimetic

    PubMed Central

    Luo, Chaosheng; Wang, Zhen; Huang, Yong

    2015-01-01

    Enantioselective α-alkylation of carbonyl is considered as one of the most important processes for asymmetric synthesis. Common alkylation agents, that is, alkyl halides, are notorious substrates for both Lewis acids and organocatalysts. Recently, olefins emerged as a benign alkylating species via photo/radical mechanisms. However, examples of enantioselective alkylation of aldehydes/ketones are scarce and direct asymmetric dialkylation remains elusive. Here we report an intramolecular α-cyclopropanation reaction of olefinic aldehydes to form chiral cyclopropane aldehydes. We demonstrate that an α-iodo aldehyde can function as a donor/acceptor carbene equivalent, which engages in a formal [2+1] annulation with a tethered double bond. Privileged bicyclo[3.1.0]hexane-type scaffolds are prepared in good optical purity using a chiral amine. The synthetic utility of the products is demonstrated by versatile transformations of the bridgehead formyl functionality. We expect the concept of using α-iodo iminium as a donor/acceptor carbene surrogate will find wide applications in chemical reaction development. PMID:26644194

  12. Study of the potential energy conversion efficiency of organic solar cells based on donor/acceptor heterojunctions

    NASA Astrophysics Data System (ADS)

    Geens, Wim

    2002-01-01

    Organic solar cells can offer an appealing alternative for bulk silicon solar cells due to their attractive properties such as flexibility and possibility to apply low-cost manufacturing techniques. The different types of existing organic solar cells reported in the literature have been critically assessed in terms of performance and processability, based on which it was concluded that the concept of the donor/acceptor bulk heterojunction sandwiched between a transparent and a metal electrode has the most potential. In order to gain more insight into the charge transport properties of spin-cast photovoltaic conjugated polymer/fullerene blends, these films were incorporated into field-effect transistors to derive values for the electron and hole mobilities. Model calculations showed that increasing these mobility values in combination with the use of thicker active layers could significantly enhance the short-circuit current density of the bulk heterojunction solar cells. Optimisation of the charge transport is required and was realised in this study by choosing PPV-oligomers and C60 as well-defined building blocks to construct the donor/acceptor networks. First, these materials were spin-cast in single-layer diodes to allow full electrical characterisation, which was then compared with simulation of the devices in dark as well as under illumination. The photovoltaic performance of blended PPV-oligomer/C60 devices remained rather low due to C60-induced shunting paths and high molecular disorder. In a second part, more morphological order was obtained by using vacuum evaporation to deposit the organic materials. Besides structural characterisation of the evaporated films, the electrical behaviour of single-layer devices was investigated and the influence of interfacial layers was addressed. Photovoltaic devices based on evaporated planar heterojunctions reaching a conversion efficiency of 1.9% and exhibiting an open-circuit voltage of over 1 V were realised

  13. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors

    PubMed Central

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S.

    2016-01-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm2V−1s−1), on/off ratio (107), and other desirable field-effect properties that meet impactful OFET application requirements. PMID:27091315

  14. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors

    NASA Astrophysics Data System (ADS)

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S.

    2016-04-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm2V‑1s‑1), on/off ratio (107), and other desirable field-effect properties that meet impactful OFET application requirements.

  15. Solution-Processed Donor-Acceptor Polymer Nanowire Network Semiconductors For High-Performance Field-Effect Transistors.

    PubMed

    Lei, Yanlian; Deng, Ping; Li, Jun; Lin, Ming; Zhu, Furong; Ng, Tsz-Wai; Lee, Chun-Sing; Ong, Beng S

    2016-01-01

    Organic field-effect transistors (OFETs) represent a low-cost transistor technology for creating next-generation large-area, flexible and ultra-low-cost electronics. Conjugated electron donor-acceptor (D-A) polymers have surfaced as ideal channel semiconductor candidates for OFETs. However, high-molecular weight (MW) D-A polymer semiconductors, which offer high field-effect mobility, generally suffer from processing complications due to limited solubility. Conversely, the readily soluble, low-MW D-A polymers give low mobility. We report herein a facile solution process which transformed a lower-MW, low-mobility diketopyrrolopyrrole-dithienylthieno[3,2-b]thiophene (I) into a high crystalline order and high-mobility semiconductor for OFETs applications. The process involved solution fabrication of a channel semiconductor film from a lower-MW (I) and polystyrene blends. With the help of cooperative shifting motion of polystyrene chain segments, (I) readily self-assembled and crystallized out in the polystyrene matrix as an interpenetrating, nanowire semiconductor network, providing significantly enhanced mobility (over 8 cm(2)V(-1)s(-1)), on/off ratio (10(7)), and other desirable field-effect properties that meet impactful OFET application requirements. PMID:27091315

  16. Construction of an Artificial Ferrimagnetic Lattice by Lithium Ion Insertion into a Neutral Donor/Acceptor Metal-Organic Framework.

    PubMed

    Taniguchi, Kouji; Narushima, Keisuke; Mahin, Julien; Kosaka, Wataru; Miyasaka, Hitoshi

    2016-04-18

    Construction of a molecular system in which the magnetic lattice exhibits long-range order is one of the fundamental goals in materials science. In this study, we demonstrate the artificial construction of a ferrimagnetic lattice by doping electrons into acceptor sites of a neutral donor/acceptor metal-organic framework (D/A-MOF). This doping was achieved by the insertion of Li-ions into the D/A-MOF, which was used as the cathode of a Li-ion battery cell. The neutral D/A-MOF is a layered system composed of a carboxylate-bridged paddlewheel-type diruthenium(II,II) complex as the donor and a TCNQ derivative as the acceptor. The ground state of the neutral form was a magnetically disordered paramagnetic state. Upon discharge of the cell, spontaneous magnetization was induced; the transition temperature was variable. The stability of the magnetically ordered lattice depended on the equilibrium electric potential of the D/A-MOF cathode, which reflected the electron-filling level. PMID:26990927

  17. Photochemical activity of a key donor-acceptor complex can drive stereoselective catalytic α-alkylation of aldehydes

    NASA Astrophysics Data System (ADS)

    Arceo, Elena; Jurberg, Igor D.; Álvarez-Fernández, Ana; Melchiorre, Paolo

    2013-09-01

    Asymmetric catalytic variants of sunlight-driven photochemical processes hold extraordinary potential for the sustainable preparation of chiral molecules. However, the involvement of short-lived electronically excited states inherent to any photochemical reaction makes it challenging for a chiral catalyst to dictate the stereochemistry of the products. Here, we report that readily available chiral organic catalysts, with well-known utility in thermal asymmetric processes, can also confer a high level of stereocontrol in synthetically relevant intermolecular carbon-carbon bond-forming reactions driven by visible light. A unique mechanism of catalysis is proposed, wherein the catalyst is involved actively in both the photochemical activation of the substrates (by inducing the transient formation of chiral electron donor-acceptor complexes) and the stereoselectivity-defining event. We use this approach to enable transformations that are extremely difficult under thermal conditions, such as the asymmetric α-alkylation of aldehydes with alkyl halides, the formation of all-carbon quaternary stereocentres and the control of remote stereochemistry.

  18. Efficient end-capping synthesis of neutral donor-acceptor [2]rotaxanes under additive-free and mild conditions.

    PubMed

    Domoto, Yuya; Sase, Shohei; Goto, Kei

    2014-11-24

    Efficient end-capping synthesis of neutral donor-acceptor (D-A) [2]rotaxanes without loading any catalysts or activating agents was achieved by utilizing high reactivity of a pentacoordinated hydrosilane toward salicylic acid derivatives. As components of [2]rotaxanes, an electron-deficient naphthalenediimide-containing axle with a salicylic acid terminus and several electron-rich bis(naphthocrown) ether macrocycles were employed. End-capping reactions with the pentacoordinated hydrosilane underwent smoothly even at low temperature to afford the corresponding [2]rotaxanes in good yields. A [2]rotaxane containing bis-1,5-(dinaphtho)-38-crown-10 ether as a wheel molecule was synthesized and isolated in 84% yield by the end-capping at -10 °C, presenting the highest yield ever reported for the end-capping synthesis of a neutral D-A [2]rotaxane. It was found that the yields of the [2]rotaxanes in the end-capping reactions were almost parallel to the formation ratios of the corresponding pseudo[2]rotaxanes estimated by utilizing model systems. These results indicate that the end-capping reaction using the pentacoordinated hydrosilane proceeded without perturbing the threading process, and most of the pseudo[2]rotaxanes underwent efficient end-capping reaction even at low temperature. PMID:25284148

  19. Two-photon absorption and spectroscopy of the lowest two-photon transition in small donor-acceptor-substituted organic molecules

    NASA Astrophysics Data System (ADS)

    Beels, Marten T.; Biaggio, Ivan; Reekie, Tristan; Chiu, Melanie; Diederich, François

    2015-04-01

    We determine the dispersion of the third-order polarizability of small donor-acceptor substituted organic molecules using wavelength-dependent degenerate four-wave mixing experiments in solutions with varying concentrations. We find that donor-acceptor-substituted molecules that are characterized by extremely efficient off-resonant nonlinearities also have a correspondingly high two-photon absorption cross section. The width and shape of the first two-photon resonance for these noncentrosymmetric molecules follows what is expected from their longest wavelength absorption peak, and the observed two-photon absorption cross sections are record high when compared to the available literature data, the size of the molecule, and the fundamental limit for two-photon absorption to the lowest excited state, which is essentially determined by the number of conjugated electrons and the excited-state energies. The two-photon absorption of the smallest molecule, which only has 16 electrons in its conjugated system, is one order of magnitude larger than for the molecule called AF-50, a reference molecule for two-photon absorption [O.-K. Kim et al., Chem. Mater. 12, 284 (2000), 10.1021/cm990662r].

  20. Thiadiazolo[3,4-c]pyridine as an Acceptor toward Fast-Switching Green Donor-Acceptor-Type Electrochromic Polymer with Low Bandgap.

    PubMed

    Ming, Shouli; Zhen, Shijie; Lin, Kaiwen; Zhao, Li; Xu, Jingkun; Lu, Baoyang

    2015-06-01

    Thiadiazolo[3,4-c]pyridine (PT), an important analog of benzothiadiazole (BT), has most recently been explored as a novel electron acceptor. It exhibits more electron-accepting ability and other unique properties and potential advantages over BT, thus inspiring us to investigate PT-based donor-acceptor-type (D-A) conjugated polymer in electrochromics. Herein, PT was employed for the rational design of novel donor-acceptor-type systems to yield a neutral green electrochromic polymer poly(4,7-di(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-[1,2,5] thiadiazolo[3,4-c]pyridine) (PEPTE). PEPTE revealed a lower bandgap (Eg,ele=0.85 eV, Eg,opt=1.12 eV) than its BT analog and also favorable redox activity and stability. Furthermore, electrochromic kinetic studies demonstrated that PEPTE displayed higher coloration efficiency than BT analog, good optical memory, and very fast switching time (0.3 s at all three wavelengths), indicating that PT would probably be a promising choice for developing novel neutral green electrochromic polymers by matching with various donor units. PMID:25955881

  1. Exquisite 1D Assemblies Arising from Rationally Designed Asymmetric Donor-Acceptor Architectures Exhibiting Aggregation-Induced Emission as a Function of Auxiliary Acceptor Strength.

    PubMed

    Singh, Roop Shikha; Mukhopadhyay, Sujay; Biswas, Arnab; Pandey, Daya Shankar

    2016-01-11

    One-dimensional nanostructures with aggregation-induced emission (AIE) properties have been fabricated to keep the pace with growing demand from optoelectronics applications. The compounds 2-[4-(4-methylpiperazin-1-yl)benzylidene]malononitrile (PM1), 2-{4-[4-(pyridin-2-yl)piperazin-1-yl]-benzylidene}malononitrile (PM2), and 2-{4-[4-(pyrimidin-2-yl)piperazin-1-yl]benzylidene}malononitrile (PM3) have been designed and synthesized by melding piperazine and dicyanovinylene to investigate AIE in an asymmetric donor-acceptor (D-A) construct of A'-D-π-A- topology. The synthetic route has been simplified by using phenylpiperazine as a weak donor (D), dicyanovinylene as an acceptor (A), and pyridyl/pyrimidyl groups (PM2/PM3) as auxiliary acceptors (A'). It has been established that A' plays a vital role in triggering AIE in these compounds because the same D-A construct led to aggregation-caused quenching upon replacing A' with an electron-donating ethyl group (PM1). Moreover, the effect of restricted intramolecular rotation and twisted intramolecular charge transfer on the mechanism of AIE has also been investigated. Furthermore, it has been clearly shown that the optical disparities of these A'-D-π-A architectures are a direct consequence of comparative A' strength. Single-crystal X-ray analyses provided justification for role of intermolecular interactions in aggregate morphology. Electrochemical and theoretical studies affirmed the effect of the A' strength on the overall properties of the A'-D-π-A system. PMID:26615814

  2. Energy transfer within self-assembled cyclic multichromophoric arrays based on orthogonally arranged donor-acceptor building blocks.

    PubMed

    Karakostas, Nikolaos; Kaloudi-Chantzea, Antonia; Martinou, Elisabeth; Seintis, Kostas; Pitterl, Florian; Oberacher, Herbert; Fakis, Mihalis; Kallitsis, Joannis K; Pistolis, George

    2015-01-01

    We herein present the coordination-driven supramolecular synthesis and photophysics of a [4+4] and a [2+2] assembly, built up by alternately collocated donor-acceptor chromophoric building blocks based, respectively, on the boron dipyrromethane (Bodipy) and perylene bisimide dye (PBI). In these multichromophoric scaffolds, the intensely absorbing/emitting dipoles of the Bodipy subunit are, by construction, cyclically arranged at the corners and aligned perpendicular to the plane formed by the closed polygonal chain comprising the PBI units. Steady-state and fs time-resolved spectroscopy reveal the presence of efficient energy transfer from the vertices (Bodipys) to the edges (PBIs) of the polygons. Fast excitation energy hopping - leading to a rapid excited state equilibrium among the low energy perylene-bisimide chromophores - is revealed by fluorescence anisotropy decays. The dynamics of electronic excitation energy hopping between the PBI subunits was approximated on the basis of a theoretical model within the framework of Förster energy transfer theory. All energy-transfer processes are quantitatively describable with Förster theory. The influence of structural deformations and orientational fluctuations of the dipoles in certain kinetic schemes is discussed. PMID:26396034

  3. A Donor-Acceptor Conjugated Polymer with Alternating Isoindigo Derivative and Bithiophene Units for Near-Infrared Modulated Cancer Thermo-Chemotherapy.

    PubMed

    Li, Dong-Dong; Wang, Jun-Xia; Ma, Yan; Qian, Hai-Sheng; Wang, Dong; Wang, Li; Zhang, Guobing; Qiu, Longzhen; Wang, Yu-Cai; Yang, Xian-Zhu

    2016-08-01

    Conjugated polymers containing alternating donor/acceptor units have strong and sharp absorbance peaks in near-infrared (NIR) region, which could be suitable for photothermal therapy. However, these polymers as photothermal transducers are rarely reported because of their water insolubility, which limits their applications for cancer therapy. Herein, we report the donor-acceptor conjugated polymer PBIBDF-BT with alternating isoindigo derivative (BIBDF) and bithiophene (BT) units as a novel photothermal transducer, which exhibited strong near-infrared (NIR) absorbance due to its low band gap (1.52 eV). To stabilize the conjugated polymer physiological environments, we utilized an amphiphilic copolymer, poly(ethylene glycol)-block-poly(hexyl ethylene phosphate) (mPEG-b-PHEP), to stabilize PBIBDF-BT-based nanoparticles (PBIBDF-BT@NPPPE) through a single emulsion method. The obtained nanoparticles PBIBDF-BT@NPPPE showed great stability in physiological environments and excellent photostability. Moreover, the PBIBDF-BT@NPPPE exhibited high photothermal conversion efficiency, reaching 46.7%, which is relatively high compared with those of commonly used materials for photothermal therapy. Accordingly, in vivo and in vitro experiments demonstrated that PBIBDF-BT@NPPPE exhibits efficient photothermal anticancer efficacy. More importantly, PBIBDF-BT@NPPPE could simultaneously encapsulate other types of therapeutic agents though hydrophobic interactions with the PHEP core and achieve NIR-triggered intracellular drug release and a synergistic combination therapy of thermo-chemotherapy for the treatment of cancer. PMID:27404741

  4. Fluorinated arene, imide and unsaturated pyrrolidinone based donor acceptor conjugated polymers: Synthesis, structure-property and device studies

    NASA Astrophysics Data System (ADS)

    Liyanage, Arawwawala Don Thilanga

    After the discovery of doped polyacetylene, organic semiconductor materials are widely studied as high impending active components in consumer electronics. They have received substantial consideration due to their potential for structural tailoring, low cost, large area and mechanically flexible alternatives to common inorganic semiconductors. To acquire maximum use of these materials, it is essential to get a strong idea about their chemical and physical nature. Material chemist has an enormous role to play in this novel area, including development of efficient synthetic methodologies and control the molecular self-assembly and (opto)-electronic properties. The body of this thesis mainly focuses on the substituent effects: how different substituents affect the (opto)-electronic properties of the donor-acceptor (D-A) conjugated polymers. The main priority goes to understand, how different alkyl substituent effect to the polymer solubility, crystallinity, thermal properties (e.g.: glass transition temperature) and morphological order. Three classes of D-A systems were extensively studied in this work. The second chapter mainly focuses on the synthesis and structure-property study of fluorinated arene (TFB) base polymers. Here we used commercially available 1,4-dibromo-2,3,5,6-tetrafluorobenzene (TFB) as the acceptor material and prepare several polymers using 3,3'-dialkyl(3,3'-R2T2) or 3,3'-dialkoxy bithiophene (3,3'-RO2T2) units as electron donors. A detail study was done using 3,3'-bithiophene donor units incorporating branched alkoxy-functionalities by systematic variation of branching position and chain length. The study allowed disentangling the branching effects on (i) aggregation tendency, intermolecular arrangement, (iii) solid state optical energy gaps, and (iv) electronic properties in an overall consistent picture, which might guide future polymer synthesis towards optimized materials for opto-electronic applications. The third chapter mainly focused on

  5. Generation of a Multicomponent Library of Disulfide Donor-Acceptor Architectures Using Dynamic Combinatorial Chemistry

    PubMed Central

    Drożdż, Wojciech; Kołodziejski, Michał; Markiewicz, Grzegorz; Jenczak, Anna; Stefankiewicz, Artur R.

    2015-01-01

    We describe here the generation of new donor-acceptor disulfide architectures obtained in aqueous solution at physiological pH. The application of a dynamic combinatorial chemistry approach allowed us to generate a large number of new disulfide macrocyclic architectures together with a new type of [2]catenanes consisting of four distinct components. Up to fifteen types of structurally-distinct dynamic architectures have been generated through one-pot disulfide exchange reactions between four thiol-functionalized aqueous components. The distribution of disulfide products formed was found to be strongly dependent on the structural features of the thiol components employed. This work not only constitutes a success in the synthesis of topologically- and morphologically-complex targets, but it may also open new horizons for the use of this methodology in the construction of molecular machines. PMID:26193265

  6. Donor-acceptor pair recombination luminescence from monoclinic Cu2SnS3 thin film

    NASA Astrophysics Data System (ADS)

    Aihara, Naoya; Tanaka, Kunihiko; Uchiki, Hisao; Kanai, Ayaka; Araki, Hideaki

    2015-07-01

    The defect levels in Cu2SnS3 (CTS) were investigated using photoluminescence (PL) spectroscopy. A CTS thin film was prepared on a soda-lime glass/molybdenum substrate by thermal co-evaporation and sulfurization. The crystal structure was determined to be monoclinic, and the compositional ratios of Cu/Sn and S/Metal were determined to be 1.8 and 1.2, respectively. The photon energy of the PL spectra observed from the CTS thin film was lower than that previously reported. All fitted PL peaks were associated with defect related luminescence. The PL peaks observed at 0.843 and 0.867 eV were assigned to donor-acceptor pair recombination luminescence, the thermal activation energies of which were determined to be 22.9 and 24.8 meV, respectively.

  7. Rapid Energy Transfer Enabling Control of Emission Polarization in Perylene Bisimide Donor-Acceptor Triads.

    PubMed

    Menelaou, Christopher; ter Schiphorst, Jeroen; Kendhale, Amol M; Parkinson, Patrick; Debije, Michael G; Schenning, Albertus P H J; Herz, Laura M

    2015-04-01

    Materials showing rapid intramolecular energy transfer and polarization switching are of interest for both their fundamental photophysics and potential for use in real-world applications. Here, we report two donor-acceptor-donor triad dyes based on perylene-bisimide subunits, with the long axis of the donors arranged either parallel or perpendicular to that of the central acceptor. We observe rapid energy transfer (<2 ps) and effective polarization control in both dye molecules in solution. A distributed-dipole Förster model predicts the excitation energy transfer rate for the linearly arranged triad but severely underestimates it for the orthogonal case. We show that the rapid energy transfer arises from a combination of through-bond coupling and through-space transfer between donor and acceptor units. As they allow energy cascading to an excited state with controllable polarization, these triad dyes show high potential for use in luminescent solar concentrator devices. PMID:26262968

  8. Thermally stable and efficient polymer solar cells based on a novel donor-acceptor copolymer.

    PubMed

    Synooka, O; Eberhardt, K-R; Balko, J; Thurn-Albrecht, T; Gobsch, G; Mitchell, W; Berny, S; Carrasco-Orozco, M; Hoppe, H

    2016-06-24

    We report high photovoltaic performance of a novel donor-acceptor (D-A) conjugated polymer poly[2,6[4,8-bis(2-ethyl-hexyl)benzo[1,2-b;4,5-b']dithiophene-co-2,5-thiophene-co-4,7[5,6-bis-octyloxy-benzo[1,2,5]thiadiazole]-co-2,5-thiophene] (PBDTTBTZT) in bulk heterojunctions with [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM). A power conversion efficiency (PCE) of more than 7% is obtained for optimized charge-extracting electrodes. Upon application of thermal stress via annealing, a superior thermal stability is demonstrated as compared to poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT). PMID:27242024

  9. Donor-acceptor-pair emission in fluorescent 4H-SiC grown by PVT method

    SciTech Connect

    Liu, Xi Zhuo, Shi-Yi; Gao, Pan; Huang, Wei; Yan, Cheng-Feng; Shi, Er-Wei

    2015-04-15

    Fluorescent SiC, which contains donor and acceptor impurities with optimum concentrations, can work as a phosphor for visible light emission by donor-acceptor-pair (DAP) recombination. In this work, 3 inch N-B-Al co-doped fluorescent 4H-SiC crystals are prepared by PVT method. The p-type fluorescent 4H-SiC with low aluminum doping concentration can show intensive yellow-green fluorescence at room temperature. N-B DAP peak wavelength shifts from 578nm to 525nm and weak N-Al DAP emission occurred 403/420 nm quenches, when the temperature increases from 4K to 298K. The aluminum doping induces higher defect concentration in the fluorescent crystal and decreases optical transmissivity of the crystal in the visible light range. It triggers more non-radiative recombination and light absorption losses in the crystal.

  10. Donor-acceptor-pair emission in fluorescent 4H-SiC grown by PVT method

    NASA Astrophysics Data System (ADS)

    Liu, Xi; Zhuo, Shi-Yi; Gao, Pan; Huang, Wei; Yan, Cheng-Feng; Shi, Er-Wei

    2015-04-01

    Fluorescent SiC, which contains donor and acceptor impurities with optimum concentrations, can work as a phosphor for visible light emission by donor-acceptor-pair (DAP) recombination. In this work, 3 inch N-B-Al co-doped fluorescent 4H-SiC crystals are prepared by PVT method. The p-type fluorescent 4H-SiC with low aluminum doping concentration can show intensive yellow-green fluorescence at room temperature. N-B DAP peak wavelength shifts from 578nm to 525nm and weak N-Al DAP emission occurred 403/420 nm quenches, when the temperature increases from 4K to 298K. The aluminum doping induces higher defect concentration in the fluorescent crystal and decreases optical transmissivity of the crystal in the visible light range. It triggers more non-radiative recombination and light absorption losses in the crystal.

  11. Thermally stable and efficient polymer solar cells based on a novel donor-acceptor copolymer

    NASA Astrophysics Data System (ADS)

    Synooka, O.; Eberhardt, K.-R.; Balko, J.; Thurn-Albrecht, T.; Gobsch, G.; Mitchell, W.; Berny, S.; Carrasco-Orozco, M.; Hoppe, H.

    2016-06-01

    We report high photovoltaic performance of a novel donor-acceptor (D-A) conjugated polymer poly[2,6[4,8-bis(2-ethyl-hexyl)benzo[1,2-b4,5-b‧]dithiophene-co-2,5-thiophene-co-4,7[5,6-bis-octyloxy-benzo[1,2,5]thiadiazole]-co-2,5-thiophene] (PBDTTBTZT) in bulk heterojunctions with [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM). A power conversion efficiency (PCE) of more than 7% is obtained for optimized charge-extracting electrodes. Upon application of thermal stress via annealing, a superior thermal stability is demonstrated as compared to poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4‧,7‧-di-2-thienyl-2‧,1‧,3‧-benzothiadiazole)] (PCDTBT).

  12. Complexes due to donor-acceptor-type transitions in GaAs

    SciTech Connect

    Reynolds, D.C.; Litton, C.W.; Almassy, R.J.; McCoy, G.L.; Nam, S.B.

    1980-09-01

    A sharp line transition at 1.51385 eV has been observed in the photoluminescence spectra of an epitaxially grown crystal of GaAs. A Si/sub 3/N/sub 4/ cap was applied by plasma deposition and the crystal was then annealed at 850 /sup 0/C for 15 min. The sharp emission line was observed after annealing. This transition was analyzed in perturbing magnetic and strain fields and is shown to result from a donor-acceptor-type complex. Three additional sharp line transitions are reported and the behavior of all of these transitions is compared with the behavior of similar transitions reported in the literature. Models for the complexes involved are re-examined and components of the complexes are suggested. All of the sharp line transitions were introduced in the growing process with the exception of the 1.51385-eV line which was introduced in the capping and annealing process.

  13. Design and synthesis of donor-acceptor Stenhouse adducts: a visible light photoswitch derived from furfural.

    PubMed

    Helmy, Sameh; Oh, Saemi; Leibfarth, Frank A; Hawker, Craig J; Read de Alaniz, Javier

    2014-12-01

    The development of an easily synthesized, modular, and tunable organic photoswitch that responds to visible light has been a long-standing pursuit. Herein we provide a detailed account of the design and synthesis of a new class of photochromes based on furfural, termed donor-acceptor Stenhouse adducts (DASAs). A wide variety of these derivatives are easily prepared from commercially available starting materials, and their photophysical properties are shown to be dependent on the substituents of the push-pull system. Analysis of the switching behavior provides conditions to access the two structural isomers of the DASAs, reversibly switch between them, and use their unique solubility behavior to provide dynamic phase-transfer materials. Overall, these negative photochromes respond to visible light and heat and display an unprecedented level of structural modularity and tunabilty. PMID:25390619

  14. Characterization of the donor-acceptor-pair transition in Nitrogen-implanted zinc oxide

    SciTech Connect

    Stichtenoth, D.; Duerr, J.; Ronning, C.; Wischmeier, L.; Voss, T.

    2008-04-15

    Zinc oxide bulk crystals were doped with nitrogen by ion beam implantation. After postimplantation annealing, a luminescent transition appears at 3.230 eV. Power-dependent photoluminescence studies and time-resolved measurements at several spectral positions within this band can be described by a model for donor-acceptor-pair (DAP) transitions. By tracing the luminescence in a temperature-dependent study, a connection to phonon replicas could be excluded. Based on these results, this luminescence line could be clearly assigned to a DAP transition. In order to increase the doping efficiency, various approaches are considered and discussed. A slight increase could be obtained by high-temperature implantation without postimplantation annealing.

  15. Ultrafast Photoinduced Charge Separation Leading to High-Energy Radical Ion-Pairs in Directly Linked Corrole-C60 and Triphenylamine-Corrole-C60 Donor-Acceptor Conjugates.

    PubMed

    Sudhakar, Kolanu; Gokulnath, Sabapathi; Giribabu, Lingamallu; Lim, Gary N; Trâm, Tạ; D'Souza, Francis

    2015-12-01

    Closely positioned donor-acceptor pairs facilitate electron- and energy-transfer events, relevant to light energy conversion. Here, a triad system TPACor-C60 , possessing a free-base corrole as central unit that linked the energy donor triphenylamine (TPA) at the meso position and an electron acceptor fullerene (C60) at the β-pyrrole position was newly synthesized, as were the component dyads TPA-Cor and Cor-C60. Spectroscopic, electrochemical, and DFT studies confirmed the molecular integrity and existence of a moderate level of intramolecular interactions between the components. Steady-state fluorescence studies showed efficient energy transfer from (1) TPA* to the corrole and subsequent electron transfer from (1) corrole* to fullerene. Further studies involving femtosecond and nanosecond laser flash photolysis confirmed electron transfer to be the quenching mechanism of corrole emission, in which the electron-transfer products, the corrole radical cation (Cor(⋅+) in Cor-C60 and TPA-Cor(⋅+) in TPACor-C60) and fullerene radical anion (C60(⋅-)), could be spectrally characterized. Owing to the close proximity of the donor and acceptor entities in the dyad and triad, the rate of charge separation, kCS , was found to be about 10(11)  s(-1), suggesting the occurrence of an ultrafast charge-separation process. Interestingly, although an order of magnitude slower than kCS , the rate of charge recombination, kCR , was also found to be rapid (kCR ≈10(10)  s(-1)), and both processes followed the solvent polarity trend DMF>benzonitrile>THF>toluene. The charge-separated species relaxed directly to the ground state in polar solvents while in toluene, formation of (3) corrole* was observed, thus implying that the energy of the charge-separated state in a nonpolar solvent is higher than the energy of (3) corrole* being about 1.52 eV. That is, ultrafast formation of a high-energy charge-separated state in toluene has been achieved in these closely spaced corrole

  16. Fundamental Studies on Donor-acceptor Conjugated Polymers Containing 'Heavy' Group 14 and Group 16 Elements

    NASA Astrophysics Data System (ADS)

    Gibson, Gregory Laird

    One advantage of conjugated polymers as organic materials is that their properties may be readily tuned through covalent modifications. This thesis presents studies on the structure-property relationships resulting from single- and double-atom substitutions on an alternating donor-acceptor conjugated polymer. Specifically, single selenium and tellurium atoms have been incorporated into the acceptor monomer in place of sulfur; silicon and germanium atoms have been substituted in place of carbon at the donor monomer bridge position. The carbon-donor/ tellurium-acceptor polymer was synthesized by a post-polymerization reaction sequence and demonstrated the utility of heavy group 16 atoms to red shift a polymer absorption spectrum. Density functional theory calculations point to a new explanation for this result invoking the lower heavy atom ionization energy and reduced aromaticity of acceptor monomers containing selenium and tellurium compared to sulfur. Absorption and emission experiments demonstrate that both silicon and germanium substitutions in the donor slightly blue shift the polymer absorption spectrum. Polymers containing sulfur in the acceptor are the strongest light absorbers of all polymers studied here. Molecular weight and phenyl end capping studies show that molecular weight appears to affect polymer absorption to the greatest degree in a medium molecular weight regime and that these effects have a significant aggregation component. Solar cell devices containing either the silicon- or germanium-donor/selenium-acceptor polymer display improved red light harvesting or hole mobility relative to their structural analogues. Overall, these results clarify the effects of single atom substitution on donor-acceptor polymers and aid in the future design of polymers containing heavy atoms.

  17. Role of donor-acceptor macrocycles in sequence specific peptide recognition and their optoelectronic properties: a detailed computational insight.

    PubMed

    Bandyopadhyay, Arkamita; Pati, Swapan K

    2016-07-27

    In this study, we have considered an experimentally synthesized organic donor-acceptor (D-A) macrocycle (CPP-TCAQ) and have modified it by incorporating different acceptor groups. We have performed density functional theory and classical molecular dynamics studies on these D-A macrocycles. We have clearly shown that cyclo[10]paraphenylene-2,6-tetracyanoanthraquinodimethanylene (CPP-TCAQ) isomers interact specifically with one particular peptide sequence tyr-leu-ala, over its structural isomer, tyr-ala-leu. However, other functionalized macrocycles bind to the tyr-ala-leu peptide sequence over tyr-leu-ala. Our calculations show that the presence of hydrogen bonds as well as π-π interactions responsible for this specific selection. Interestingly, it is the additional charge transfer induced dipolar interactions that favour binding of the tripeptide with the bulky C-terminal leucine amino acid, tyr-ala-leu. We confirmed that these host-guest complexes are stable in water medium as well as at room temperature. Thus, these hosts can bind effectively to any protein fragment bearing a particular tripeptide. Interestingly, the macrocycle, which recognizes the peptide sequence with a bulky C-terminal amino acid, also shows photophysical properties. The reasons for this happen to be the same (dipolar interactions introduce dipole allowed states for optical absorption as well as attracting the oppositely oriented dipolar groups). Recognition of the peptide sequence with a bulky C-terminal group is carried out for the first time with this functionalised macrocycle, which in addition shows photophysical properties. PMID:27412849

  18. Electrochromism of a fused acceptor-donor-acceptor triad covering entire UV-vis and near-infrared regions.

    PubMed

    Yao, Bin; Ye, Xichong; Zhang, Jie; Wan, Xinhua

    2014-10-17

    A novel fused acceptor-donor-acceptor (A-D-A) type panchromatically electrochromic compound was synthesized. It exhibited intensive absorption bands covering entire UV-vis and near-infrared regions upon reduction to the radical anionic state, owing to the simultaneous presence of π*-π* transitions and intervalence charge transfer. PMID:25268224

  19. Enhanced Visible Photovoltaic Response of TiO₂ Thin Film with an All-Inorganic Donor-Acceptor Type Polyoxometalate.

    PubMed

    Li, Jian-Sheng; Sang, Xiao-Jing; Chen, Wei-Lin; Zhang, Lan-Cui; Zhu, Zai-Ming; Ma, Teng-Ying; Su, Zhong-Min; Wang, En-Bo

    2015-06-24

    In the field of material chemistry, it is of great significance to develop abundant and sustainable materials for solar energy harvesting and management. Herein, after evaluating the energy band characteristics of 13 kinds of polyoxometalates (POMs), the trisubstituted POM compound K6H4[α-SiW9O37Co3(H2O)3]·17H2O (SiW9Co3) was first studied due to its relatively smaller band gap (2.23 eV) and higher lowest unoccupied molecular orbital (LUMO) level (-0.63 V vs NHE). Additionally, the preliminary computational modeling indicated that SiW9Co3 exhibited the donor-acceptor (D-A) structure, in which the cobalt oxygen clusters and tungsten skeletons act as the electron donor and electron acceptor, respectively. By employing SiW9Co3 to modify the TiO2 film, the visible photovoltaic and photocurrent response were both enhanced, and the light-induced photocurrent at 420 nm was improved by 7.1 times. Moreover, the highly dispersive and small sized SiW9Co3 nanoclusters loading on TiO2 were successfully achieved by fabricating the nanocomposite film of {TiO2/SiW9Co3}3 with the layer-by-layer method, which can result in the photovoltaic performance enhancement of dye-sensitized solar cells (DSSCs), of which the overall power conversion efficiency was improved by 25.6% from 6.79% to 8.53% through the synergistic effect of POMs and Ru-complex. PMID:26030670

  20. Proficiency of acceptor-donor-acceptor organic dye with spiro-MeOTAD HTM on the photovoltaic performance of dye sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Ramavenkateswari, K.; Venkatachalam, P.

    2016-08-01

    This work investigates the proficiency of acceptor-donor-acceptor (A-D-A) organic dye Diisopropyl azodicarboxylate (DIAC) as photosensitizer on the photovoltaic parameters of silver (Ag) doped TiO2 photoanode dye-sensitized solar cells (DSSCs) with quasi-solid state electrolyte/hole transport material (HTM) spiro-MeOTAD. TNSs (TiO2 nanosticks) photoanodes are prepared through sol-gel method and hydrothermal technique. X-ray powder diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM) and BET measurement were used to characterize the structure and morphology of TiO2 nanostructures. The Diisopropyl azodicarboxylate organic dye with TNPs-Ag@TNSs composite photoanode structure and spiro-MeOTAD HTM exhibited better power conversion efficiency (PCE). [Figure not available: see fulltext.

  1. Achieving near-infrared emission in platinum(ii) complexes by using an extended donor-acceptor-type ligand.

    PubMed

    Zhang, You-Ming; Meng, Fanyuan; Tang, Jian-Hong; Wang, Yafei; You, Caifa; Tan, Hua; Liu, Yu; Zhong, Yu-Wu; Su, Shijian; Zhu, Weiguo

    2016-03-15

    A series of C^N ligands with donor-acceptor (D-A) frameworks, i.e. TPA-BTPy, TPA-BTPy-Fl and Fl(TPA-BTPy)2, as well as their mono- and di-nuclear platinum(ii) complexes of (TPA-BTPy)Pt(pic), (TPA-BTPy-Fl)Pt(pic) and [Fl(TPA-BTPy)2]Pt2(pic)2 are respectively designed and synthesized, in which triphenylamine (TPA) and fluorene (Fl) are used as the D units, 4-(pyrid-2-yl)benzothiadiazole (BTPy) as the A unit, and the picolinate anion (pic) as the auxiliary ligand. Their thermal, photophysical and electrochemical characteristics were investigated. Compared to mono-nuclear platinum complexes and their free ligands, this dinuclear one of [Fl(TPA-BTPy)2]Pt2(pic)2 shows an obvious interaction from the platinum atom to ligand and dual emission peaks at 828 and 601 nm in thin films. Upon oxidation with antimony pentachloride in dichloromethane, charge transfer transitions between the platinum and ligand are observed for the three complexes. The single-emissive-layer polymer light-emitting devices doped with [Fl(TPA-BTPy)2]Pt2(pic)2 display a strong electroluminescence with dual emission peaks at 780 and 600 nm at a dopant concentration over 4 wt%. A maximum external quantum efficiency of 0.02% with a radiance of 59 μW cm(-2) is obtained in the device at 30 wt% dopant concentration. This work indicates that the use of an extended D-A-type ligand is an effective strategy to achieve NIR emission for platinum complexes in PLEDs. PMID:26880278

  2. Comparison of fluctuating potentials and donor-acceptor pair transitions in a Cu-poor Cu{sub 2}ZnSnS{sub 4} based solar cell

    SciTech Connect

    Teixeira, J. P.; Sousa, R. A.; Sousa, M. G.; Cunha, A. F. da; Leitão, J. P.; Fernandes, P. A.; Salomé, P. M. P.; González, J. C.

    2014-10-20

    The structure of the electronic energy levels of a single phase Cu{sub 2}ZnSnS{sub 4} film, as confirmed by Raman Scattering and x-ray diffraction, is investigated through a dependence on the excitation power of the photoluminescence (PL). The behavior of the observed asymmetric band, with a peak energy at ∼1.22 eV, is compared with two theoretical models: (i) fluctuating potentials and (ii) donor-acceptor pair transitions. It is shown that the radiative recombination channels in the Cu-poor film are strongly influenced by tail states in the bandgap as a consequence of a heavy doping and compensation levels. The contribution of the PL for the evaluation of secondary phases is also highlighted.

  3. Donor-acceptor-structured 1,4-diazatriphenylene derivatives exhibiting thermally activated delayed fluorescence: design and synthesis, photophysical properties and OLED characteristics

    NASA Astrophysics Data System (ADS)

    Takahashi, Takehiro; Shizu, Katsuyuki; Yasuda, Takuma; Togashi, Kazunori; Adachi, Chihaya

    2014-06-01

    A new series of luminescent 1,4-diazatriphenylene (ATP) derivatives with various peripheral donor units, including phenoxazine, 9,9-dimethylacridane and 3-(diphenylamino)carbazole, is synthesized and characterized as thermally activated delayed fluorescence (TADF) emitters. The influence of the donor substituents on the electronic and photophysical properties of the materials is investigated by theoretical calculations and experimental spectroscopic measurements. These ATP-based molecules with donor-acceptor-donor (D-A-D) structures can reduce the singlet-triplet energy gap (0.04-0.26 eV) upon chemical modification of the ATP core, and thus exhibit obvious TADF characteristics in solution and doped thin films. As a demonstration of the potential of these materials, organic light-emitting diodes containing the D-A-D-structured ATP derivatives as emitters are fabricated and tested. External electroluminescence quantum efficiencies above 12% and 8% for green- and sky-blue-emitting devices, respectively, are achieved.

  4. High-Resolution Kelvin Probe Force Microscopy Imaging of Interface Dipoles and Photogenerated Charges in Organic Donor-Acceptor Photovoltaic Blends.

    PubMed

    Fuchs, Franz; Caffy, Florent; Demadrille, Renaud; Mélin, Thierry; Grévin, Benjamin

    2016-01-26

    We present noncontact atomic force microscopy and Kelvin probe force microscopy studies of nanophase segregated photovoltaic blends based on an oligothiophene-fluorenone oligomer and [6,6]-phenyl C70 butyric acid methyl ester. We carried out a complete analysis of the influence of the tip-surface interaction regime on the topographic, in-dark contact potential and surface photovoltage contrasts. It is demonstrated that an optimal lateral resolution is achieved for all channels below the onset of a contrast in the damping images. With the support of electrostatic simulations, it is shown that in-dark contact potential difference contrasts above subsurface acceptor clusters are consistent with an uneven distribution of permanent charges at the donor-acceptor interfaces. A remarkable dependence of the surface photovoltage magnitude with respect to the tip-surface distance is evidenced and attributed to a local enhancement of the electromagnetic field at the tip apex. PMID:26750993

  5. Organic donor-acceptor assemblies form coaxial p-n heterojunctions with high photoconductivity.

    PubMed

    Prasanthkumar, Seelam; Ghosh, Samrat; Nair, Vijayakumar C; Saeki, Akinori; Seki, Shu; Ajayaghosh, Ayyappanpillai

    2015-01-12

    The formation of coaxial p-n heterojunctions by mesoscale alignment of self-sorted donor and acceptor molecules, important to achieve high photocurrent generation in organic semiconductor-based assemblies, remains a challenging topic. Herein, we show that mixing a p-type π gelator (TTV) with an n-type semiconductor (PBI) results in the formation of self-sorted fibers which are coaxially aligned to form interfacial p-n heterojunctions. UV/Vis absorption spectroscopy, powder X-ray diffraction studies, atomic force microscopy, and Kelvin-probe force microscopy revealed an initial self-sorting at the molecular level and a subsequent mesoscale self-assembly of the resulted supramolecular fibers leading to coaxially aligned p-n heterojunctions. A flash photolysis time-resolved microwave conductivity (FP-TRMC) study revealed a 12-fold enhancement in the anisotropic photoconductivity of TTV/PBI coaxial fibers when compared to the individual assemblies of the donor/acceptor molecules. PMID:25430809

  6. Multiple Charge Transfer States at Ordered and Disordered Donor/Acceptor Interfaces

    NASA Astrophysics Data System (ADS)

    Fusella, Michael; Verreet, Bregt; Lin, Yunhui; Brigeman, Alyssa; Purdum, Geoffrey; Loo, Yueh-Lin; Giebink, Noel; Rand, Barry

    The presence of charge transfer (CT) states in organic solar cells is accepted, but their role in photocurrent generation is not well understood. Here we investigate solar cells based on rubrene and C60 to show that CT state properties are influenced by molecular ordering at the donor/acceptor (D/A) interface. Crystalline rubrene films are produced with domains of 100s of microns adopting the orthorhombic phase, as confirmed by grazing incidence XRD, with the (h00) planes parallel to the substrate. C60 grown atop these films adopts a highly oriented face-centered cubic phase with the (111) plane parallel to the substrate. For this highly ordered system we have discovered the presence of four CT states. Polarized external quantum efficiency (EQE) measurements assign three of these to crystalline origins with the remaining one well aligned with the disordered CT state. Varying the thickness of a disordered blend of rubrene:C60 atop the rubrene template modulates the degree of crystallinity at the D/A interface. Strikingly, this process alters the prominence of the four CT states measured via EQE, and results in a transition from single to multiple electroluminescence peaks. These results underscore the impact of molecular structure at the heterojunction on charge photogeneration.

  7. Density of states determination in organic donor-acceptor blend layers enabled by molecular doping

    NASA Astrophysics Data System (ADS)

    Fischer, Janine; Ray, Debdutta; Kleemann, Hans; Pahner, Paul; Schwarze, Martin; Koerner, Christian; Vandewal, Koen; Leo, Karl

    2015-06-01

    Charge carrier transport is a key parameter determining the efficiency of organic solar cells, and is closely related to the density of free and trapped states. For trap characterization, impedance spectroscopy is a suitable, non-invasive method, applicable to complete organic semiconductor devices. In order to contribute to the capacitive signal, the traps must be filled with charge carriers. Typically, trap filling is achieved by illuminating the device or by injecting charge carriers through application of a forward bias voltage. However, in both cases, the exact number of charge carriers in the device is not known and depends strongly on the measurement conditions. Here, hole trap states of the model blend layer ZnPc:C60 are filled by weak p-doping, enabling trap characterization in a blend layer at a controlled hole density. We evaluate impedance spectra at different temperatures in order to determine the density of occupied states (DOOS) directly from the capacitance-frequency spectra by assuming a simple energy diagram. The reconstructed DOOS distribution is analyzed at different doping concentrations and device thicknesses and compared to thermally stimulated current measurements performed on the same devices. In both methods, a pronounced Gaussian peak at about 0.4 eV below the transport level is found as well as deep, exponential tail states, providing a deeper insight into the density of states distribution of this donor-acceptor blend layer. Additionally, the effect of doping-induced trap filling on the solar cell characteristics is studied in these devices.

  8. Oligomeric Dithienopyrrole-Thienopyrrolodione (DTP-TPD) Donor-Acceptor Copolymer for Organic Photovoltaics: Preprint

    SciTech Connect

    Hammond, S. R.; Braunecker, W.; Garcia, A.; Larsen, R.; Owczarczyk, Z.; Olson, D.; Ginley, D.

    2011-07-01

    A new donor-acceptor copolymer system based upon a dithienopyrrole (DTP) donor moiety and a thienopyrrolodione (TPD) accepting moiety has been designed and synthesized for organic photovoltaic (OPV) applications. The TPD accepting moiety has recently gained significant attention in the OPV community and is being incorporated into a number of different polymer systems. In contrast, the DTP donor moiety has received only limited attention, likely due in part to synthetic difficulties relating to the monomer. In our hands, the bis(trimethyltin)-DTP monomer was indelibly contaminated with ~5% of the mono-destannylated DTP, which limited the Stille polymerization with the dibromo-TPD monomer (>99% pure) to produce material with Mn ~ 4130 g/mol (PDI = 1.10), corresponding to around eight repeat units. Despite this limitation, UV-visible absorption spectroscopy demonstrates strong absorption for this material with a band gap of ~1.6 eV. Cyclic voltammetry indicates a highest occupied molecular orbital (HOMO) energy level of -5.3 eV, which is much lower than calculations predicted. Initial bulk heterojunction OPV devices fabricated with the fullerene acceptor phenyl C61 butyric acid methyl ester (PCBM) exhibit Voc ~ 700 mV, which supports the deep HOMO value obtained from CV. These results suggest the promise of this copolymer system.

  9. Theoretical design of solvatochromism switching by photochromic reactions using donor-acceptor disubstituted diarylethene derivatives with oxidized thiophene rings.

    PubMed

    Okuno, Katsuki; Shigeta, Yasuteru; Kishi, Ryohei; Nakano, Masayoshi

    2015-03-01

    We have designed several diarylethene derivatives with oxidized thiophene rings and donor-acceptor substituents, which show the solvatochromism switching by photochromic reactions, using a time-dependent density functional theory (TD-DFT) method using the polarizable continuum model (PCM). It is found that in the UV-vis spectral region examined only the open-ring isomers exhibit the solvatochromism, while the closed-ring isomers do not. The mechanism of the solvatochromism behavior and its switching process are clarified from the viewpoint of the charge-transfer (CT) excitation from the donor to the acceptor substituents. We demonstrate that this CT excitation can be controlled by choosing appropriate pairs of the donor and the acceptor substituents on the basis of the orbital correlation diagram between the diarylethene derivatives and the donor-acceptor substituents, which is constructed from the topologies and the orbital energies of the molecular orbitals primarily contributing to the excitations. PMID:25655363

  10. Boron(III)-Containing Donor-Acceptor Compound with Goldlike Reflective Behavior for Organic Resistive Memory Devices.

    PubMed

    Poon, Chun-Ting; Wu, Di; Yam, Vivian Wing-Wah

    2016-03-01

    A small-molecule-based boron(III)-containing donor-acceptor compound has been designed and synthesized. Interesting goldlike reflective behavior was observed in the neat thin-film sample from simple spin-coating preparation, which can serve as a potential organic thin-film optical reflector. The small thickness in nanometer range and the relatively smooth surface morphology, together with simple preparation and easy solution processability, are attractive features for opening up new avenues for the fabrication of reflective coatings. Moreover, this donor-acceptor compound has been employed in the fabrication of organic resistive memory device, which exhibited good performance with low turn-on voltage, small operating bias, large ON/OFF ratio, and long retention time. PMID:26879606

  11. Blinking fluorescence of single donor-acceptor pairs: Important role of ``dark'' states in resonance energy transfer via singlet levels

    NASA Astrophysics Data System (ADS)

    Osad'ko, I. S.; Shchukina, A. L.

    2012-06-01

    The influence of triplet levels on Förster resonance energy transfer via singlet levels in donor-acceptor (D-A) pairs is studied. Four types of D-A pair are considered: (i) two-level donor and two-level acceptor, (ii) three-level donor and two-level acceptor, (iii) two-level donor and three-level acceptor, and (iv) three-level donor and three-level acceptor. If singlet-triplet transitions in a three-level acceptor molecule are ineffective, the energy transfer efficiency E=IA/(IA+ID), where ID and IA are the average intensities of donor and acceptor fluorescence, can be described by the simple theoretical equation E(F)=FTD/(1+FTD). Here F is the rate of energy transfer, and TD is the donor fluorescence lifetime. In accordance with the last equation, 100% of the donor electronic energy can be transferred to an acceptor molecule at FTD≫1. However, if singlet-triplet transitions in a three-level acceptor molecule are effective, the energy transfer efficiency is described by another theoretical equation, E(F)=F¯(F)TD/[1+F¯(F)TD]. Here F¯(F) is a function of F depending on singlet-triplet transitions in both donor and acceptor molecules. Expressions for the functions F¯(F) are derived. In this case the energy transfer efficiency will be far from 100% even at FTD≫1. The character of the intensity fluctuations of donor and acceptor fluorescence indicates which of the two equations for E(F) should be used to find the value of the rate F. Therefore, random time instants of photon emission in both donor and acceptor fluorescence are calculated by the Monte Carlo method for all four types of D-A pair. Theoretical expressions for start-stop correlators (waiting time distributions) in donor and acceptor fluorescence are derived. The probabilities wND(t) and wNA(t) of finding N photons of donor and acceptor fluorescence in the time interval t are calculated for various values of the energy transfer rate F and for all four types of D-A pair. Comparison of the calculated D

  12. Charge carrier dynamics in organic semiconductors and their donor-acceptor composites: Numerical modeling of time-resolved photocurrent

    NASA Astrophysics Data System (ADS)

    Johnson, Brian; Kendrick, Mark J.; Ostroverkhova, Oksana

    2013-09-01

    We present a model that describes nanosecond (ns) time-scale photocurrent dynamics in functionalized anthradithiophene (ADT) films and ADT-based donor-acceptor (D/A) composites. By fitting numerically simulated photocurrents to experimental data, we quantify contributions of multiple pathways of charge carrier photogeneration to the photocurrent, as well as extract parameters that characterize charge transport (CT) in organic films including charge carrier mobilities, trap densities, hole trap depth, and trapping and recombination rates. In pristine ADT films, simulations revealed two competing charge photogeneration pathways: fast, occurring on picosecond (ps) or sub-ps time scales with efficiencies below 10%, and slow, which proceeds at the time scale of tens of nanoseconds, with efficiencies of about 11%-12%, at the applied electric fields of 40-80 kV/cm. The relative contribution of these pathways to the photocurrent was electric field dependent, with the contribution of the fast process increasing with applied electric field. However, the total charge photogeneration efficiency was weakly electric field dependent exhibiting values of 14%-20% of the absorbed photons. The remaining 80%-86% of the photoexcitation did not contribute to charge carrier generation at these time scales. In ADT-based D/A composites with 2 wt.% acceptor concentration, an additional pathway of charge photogeneration that proceeds via CT exciton dissociation contributed to the total charge photogeneration. In the composite with the functionalized pentacene (Pn) acceptor, which exhibits strong exciplex emission from a tightly bound D/A CT exciton, the contribution of the CT state to charge generation was small, ˜8%-12% of the total number of photogenerated charge carriers, dependent on the electric field. In contrast, in the composite with PCBM acceptor, the CT state contributed about a half of all photogenerated charge carriers. In both D/A composites, the charge carrier mobilities were

  13. Donor-acceptor interchange tunneling in HDO-DOH and the higher energy HDO-HOD isotopomer

    NASA Astrophysics Data System (ADS)

    Karyakin, E. N.; Fraser, G. T.; Lovas, F. J.; Suenram, R. D.; Fujitake, M.

    1995-01-01

    The microwave and submillimeter spectra of the a-type K=0←0 and K=1←1, c-type K=1←0, and isotopically allowed b-type K=1←0 bands of the O-D bonded HDO-DOH water dimer isotopomer and the higher energy O-H bonded HDO-HOD isotopomer have been measured using molecular-beam electric resonance optothermal and pulsed-nozzle Fourier-transform microwave spectrometers. The present results obtained in He and He/Ne seeded molecular beams give the first evidence for the presence of the higher energy O-H bonded mixed protonated-deuterated water dimers. These species were not reported previously in studies using seeded Ar molecular beams. The donor-acceptor interchange tunneling splittings are found to be 1322.1019(43) and 5004.059(20) MHz for the HDO-DOH and the metastable HDO-HOD dimers, respectively. For both isotopomers, the donor-accepter interchange tunneling-state selections rules for the b- and c-type bands are consistent with tunneling pathways corresponding to geared partial internal rotation of the two subunits in double-minima potentials. The larger tunneling splitting in HDO-HOD is primarily the consequence of the smaller effective reduced mass for tunneling in this system compared to that in HDO-DOH. The presence of both b- and c-type K=1←0 bands allows the direct measurement of the largest tunneling splitting, that associated with the internal rotation about the O-H-O or O-D-O bond of the nonbonded proton/deuteron on the proton donating unit. For the K=0 state of HDO-DOH this splitting is 214 208.38(23) MHz, while for the K=0 state of HDO-HOD it is 117 440.97(17) MHz. A strong b-type Coriolis interaction is observed between the upper K=0 and lower K=1 states in HDO-DOH, similar to that observed previously in (H2O)2.

  14. Theoretical Investigation of Donor-Acceptor Copolymers Based on C-, Si-, and Ge-Bridged Thieno[3,2-b]dithiophene for Organic Solar Cell Applications

    NASA Astrophysics Data System (ADS)

    Liu, Xiaorui; Huang, Chengzhi; Shen, Wei; He, Rongxing; Li, Ming

    2016-06-01

    The aim of this work is to modify the electron-donating block in donor-acceptor (D-A) copolymers to improve their electronic and photophysical properties for organic solar cell (OSC) applications. Based on the reported polymer PCPDTTTTz (Pa1), which includes electron-rich cyclopenta[2,1-b:3,4-b']dithiophene (CPDT), electron-withdrawing tetrazine, and bridge thiophene, we substituted CPDT with electron-rich dithienocyclopentadithiophene, dithienosiloledithiophene, and dithienogermolodithiophene to design three D-A copolymers (Pa2 to Pa4). The calculation results indicate that Pa3 and Pa4 show lower highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) energy levels and larger open-circuit voltage (V oc) than Pa1. Polymers Pa2 to Pa4 exhibit better performance with stronger and wider optical absorption and good hole transport properties in comparison with Pa1. The predicted power conversion efficiencies for the designed polymers Pa2 to Pa4 in OSC applications are ˜5.7%, ˜5.9%, and 6.0%, respectively. These results clearly indicate that modifying the electron-donating block in D-A copolymers can effectively improve their electronic and photophysical properties and OSC performance. The designed polymers Pa2 to Pa4 may be promising donor candidates for OSC applications.

  15. Creation of Superheterojunction Polymers via Direct Polycondensation: Segregated and Bicontinuous Donor-Acceptor π-Columnar Arrays in Covalent Organic Frameworks for Long-Lived Charge Separation.

    PubMed

    Jin, Shangbin; Supur, Mustafa; Addicoat, Matthew; Furukawa, Ko; Chen, Long; Nakamura, Toshikazu; Fukuzumi, Shunichi; Irle, Stephan; Jiang, Donglin

    2015-06-24

    By developing metallophthalocyanines and diimides as electron-donating and -accepting building blocks, herein, we report the construction of new electron donor-acceptor covalent organic frameworks (COFs) with periodically ordered electron donor and acceptor π-columnar arrays via direct polycondensation reactions. X-ray diffraction measurements in conjunction with structural simulations resolved that the resulting frameworks consist of metallophthalocyanine and diimide columns, which are ordered in a segregated yet bicontinuous manner to form built-in periodic π-arrays. In the frameworks, each metallophthalocyanine donor and diimide acceptor units are exactly linked and interfaced, leading to the generation of superheterojunctions-a new type of heterojunction machinery, for photoinduced electron transfer and charge separation. We show that this polycondensation method is widely applicable to various metallophthalocyanines and diimides as demonstrated by the combination of copper, nickel, and zinc phthalocyanine donors with pyrommellitic diimide, naphthalene diimide, and perylene diimide acceptors. By using time-resolved transient absorption spectroscopy and electron spin resonance, we demonstrated that the COFs enable long-lived charge separation, whereas the metal species, the class of acceptors, and the local geometry between donor and acceptor units play roles in determining the photochemical dynamics. The results provide insights into photoelectric COFs and demonstrate their enormous potential for charge separation and photoenergy conversions. PMID:26030399

  16. Thermally activated delayed fluorescence evidence in non-bonding transition electron donor-acceptor molecules

    NASA Astrophysics Data System (ADS)

    Marghad, Ikbal; Clochard, M. C.; Ollier, N.; Wade, Travis L.; Aymes-Chodur, C.; Renaud, C.; Zissis, G.

    2015-09-01

    The exhibition of thermally activated delayed fluorescence on triazine derivative by the introduction of a nonbonding part is demonstrated. Two molecules containing triazine core as acceptor and carbazole part as donor has been synthesized and characterized. One of these molecules bears an additional nonbonding part by the means of a phenoxy group. The results indicated that the molecule bearing the nonbonding molecular part (phenoxy) exhibit thermally activated delayed fluorescence while not on molecule free of non-bonding group. The results are supported by, photoluminescence, spectral analysis time-resolved fluorescence and time-dependent density functional estimation

  17. Triflic Acid-Catalyzed Cycloisomerization Reactions of Donor-Acceptor Cyclopropanes: Access to Alkyl 5-Arylfuran-2-carboxylates.

    PubMed

    Zhu, Yuequan; Xu, Panpan; Gong, Yuefa

    2016-06-01

    A direct synthetic strategy starting from alkyl 1-alkoxy-2-aroylcyclopropanecarboxylates was developed for the construction of alkyl 5-arylfuran-2-carboxylates. These donor-acceptor cyclopropanes smoothly undergo a simple ring-opening reaction or/and cycloisomerization reaction in the presence of acid at room temperature, which greatly depends on the properties of the acid used in the experiment. Alkyl 5-arylfuran-2-carboxylates were afforded in high yields in triflic acid, whereas alkyl 2,5-dioxo-5-phenylpentanoate became the major product in other protic acids and Lewis acids. PMID:27156857

  18. Thiophene-based donor-acceptor co-oligomers by copper-catalyzed 1,3-dipolar cycloaddition.

    PubMed

    Potratz, Stefanie; Mishra, Amaresh; Bäuerle, Peter

    2012-01-01

    Herein we present a three-component one-pot procedure to synthesize co-oligomers of a donor-acceptor-donor type, in which thiophene moieties work as donor and 1,2,3-triazoles as acceptor units. In this respect, terminally ethynylated (oligo)thiophenes were coupled to halogenated (oligo)thiophenes in the presence of sodium azide and a copper catalyst. Optoelectronic properties of various thiophene-1,2,3-triazole co-oligomers were investigated by UV-vis spectroscopy and cyclic voltammetry. Several co-oligomers were electropolymerized to the corresponding conjugated polymers. PMID:23015814

  19. New organic donor-acceptor-π-acceptor sensitizers for efficient dye-sensitized solar cells and photocatalytic hydrogen evolution under visible-light irradiation.

    PubMed

    Li, Xing; Cui, Shicong; Wang, Dan; Zhou, Ying; Zhou, Hao; Hu, Yue; Liu, Jin-Gang; Long, Yitao; Wu, Wenjun; Hua, Jianli; Tian, He

    2014-10-01

    Two organic donor-acceptor-π-acceptor (D-A-π-A) sensitizers (AQ and AP), containing quinoxaline/pyrido[3,4-b]pyrazine as the auxiliary acceptor, have been. Through fine-tuning of the auxiliary acceptor, a higher designed and synthesized photoelectric conversion efficiency of 6.02% for the AQ-based dye-sensitized solar cells under standard global AM1.5 solar conditions was achieved. Also, it was found that AQ-Pt/TiO2 photocatalysts displayed a better rate of H2 evolution under visible-light irradiation (420 nm<λ<780 nm) because of the stability of the oxidized states and the lower rates of electron recombination. Importantly, sensitizers AQ and AP-Pt/TiO2 showed strong photocatalytic activity during continuous light soaking for 10 h with methanol as the sacrificial electron donor. Additionally, the processes of their intermolecular electron transfer were further investigated theoretically by using time-dependent DFT. The calculated results indicate that the auxiliary acceptor plays the role of an electron trap and results in broad spectral responses. PMID:25154958

  20. Theoretical investigation of self-assembled donor-acceptor phthalocyanine complexes and their application in dye-sensitized solar cells.

    PubMed

    Yu, Lijuan; Lin, Li; Liu, Yuwen; Li, Renjie

    2015-06-01

    A theoretical investigation of self-assembled donor-acceptor dyads (ZnPca, ZnPcb and ZnPcc) formed by axial coordination of zinc phthalocyanines appended with 4-carboxyl pyridine has been conducted with the density functional theory (DFT) method and time-dependent DFT (TD-DFT) calculations. A comparison between the molecular structures, atomic charges, molecular orbitals, UV-vis spectra and infrared (IR) spectra has been studied. Further, as sensitizers for the TiO2-based dye-sensitized solar cells, the photovoltaic performances have been investigated. The ZnPcc-sensitized solar cell exhibits a higher conversion efficiency than the ZnPcb and ZnPca-sensitized ones under AM 1.5G solar irradiation, while the ZnPca-sensitized cell performs the poorest due to the lack of peripheral substituents (n-butyoxyl groups) which can be confirmed by the result of the theoretical research. It shows that the directionality of charge transfer in the self-assembled donor-acceptor dyads is important and benefit for the efficiency of the DSSC. PMID:25917246

  1. Acceptor and Excitation Density Dependence of the Ultrafast Polaron Absorption Signal in Donor-Acceptor Organic Solar Cell Blends.

    PubMed

    Zarrabi, Nasim; Burn, Paul L; Meredith, Paul; Shaw, Paul E

    2016-07-21

    Transient absorption spectroscopy on organic semiconductor blends for solar cells typically shows efficient charge generation within ∼100 fs, accounting for the majority of the charge carriers. In this Letter, we show using transient absorption spectroscopy on blends containing a broad range of acceptor content (0.01-50% by weight) that the rise of the polaron signal is dependent on the acceptor concentration. For low acceptor content (<10% by weight), the polaron signal rises gradually over ∼1 ps with most polarons generated after 200 fs, while for higher acceptor concentrations (>10%) most polarons are generated within 200 fs. The rise time in blends with low acceptor content was also found to be sensitive to the pump fluence, decreasing with increasing excitation density. These results indicate that the sub-100 fs rise of the polaron signal is a natural consequence of both the high acceptor concentrations in many donor-acceptor blends and the high excitation densities needed for transient absorption spectroscopy, which results in a short average distance between the exciton and the donor-acceptor interface. PMID:27355877

  2. Charge transport studies in donor-acceptor block copolymer PDPP-TNT and PC71BM based inverted organic photovoltaic devices processed in room conditions

    NASA Astrophysics Data System (ADS)

    Srivastava, Shashi B.; Sonar, Prashant; Singh, Samarendra P.

    2015-07-01

    Diketopyrrolopyrole-naphthalene polymer (PDPP-TNT), a donor-acceptor co-polymer, has shown versatile behavior demonstrating high performances in organic field-effect transistors (OFETs) and organic photovoltaic (OPV) devices. In this paper we report investigation of charge carrier dynamics in PDPP-TNT, and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) bulk-heterojunction based inverted OPV devices using current density-voltage (J-V) characteristics, space charge limited current (SCLC) measurements, capacitance-voltage (C-V) characteristics, and impedance spectroscopy (IS). OPV devices in inverted architecture, ITO/ZnO/PDPP-TNT:PC71BM/MoO3/Ag, are processed and characterized at room conditions. The power conversion efficiency (PCE) of these devices are measured ˜3.8%, with reasonably good fill-factor 54.6%. The analysis of impedance spectra exhibits electron's mobility ˜2 × 10-3 cm2V-1s-1, and lifetime in the range of 0.03-0.23 ms. SCLC measurements give hole mobility of 1.12 × 10-5 cm2V-1s-1, and electron mobility of 8.7 × 10-4 cm2V-1s-1.

  3. Donor/Acceptor Dihydroindeno[1,2-a]fluorene and Dihydroindeno[2,1-b]fluorene: Towards New Families of Organic Semiconductors.

    PubMed

    Romain, Maxime; Tondelier, Denis; Geffroy, Bernard; Jeannin, Olivier; Jacques, Emmanuel; Rault-Berthelot, Joëlle; Poriel, Cyril

    2015-06-22

    New families of donor/acceptor semiconductors based on dihydroindeno[1,2-a]fluorene and dihydroindeno[2,1-b]fluorene are reported. Due to the spiro bridges, this new generation of dihydroindenofluorenes allows a spatial separation of HOMO and LUMO, which retains the high ET value of the dihydroindenofluorene backbone and excellent physical properties. This control of the electronic and physical properties has allowed a second generation of dihydroindeno[1,2-a]fluorene to be obtained with strongly enhanced performance in green and sky-blue phosphorescent organic light-emitting diodes (PhOLEDs) relative to the first generation of materials. To date, this is the highest performance ever reported for a blue PhOLED by using a dihydroindenofluorene derivative. Through this structure-property relationship study, a remarkable difference of performance between syn and anti isomers has also been highlighted. This surprising behaviour has been attributed to the different symmetry of the two molecules, and highlights the importance of the geometry profiles in the design of host materials for PhOLEDs. PMID:26012479

  4. Charge transport studies in donor-acceptor block copolymer PDPP-TNT and PC71BM based inverted organic photovoltaic devices processed in room conditions

    SciTech Connect

    Srivastava, Shashi B.; Singh, Samarendra P.; Sonar, Prashant

    2015-07-15

    Diketopyrrolopyrole-naphthalene polymer (PDPP-TNT), a donor-acceptor co-polymer, has shown versatile behavior demonstrating high performances in organic field-effect transistors (OFETs) and organic photovoltaic (OPV) devices. In this paper we report investigation of charge carrier dynamics in PDPP-TNT, and [6,6]-phenyl C{sub 71} butyric acid methyl ester (PC71BM) bulk-heterojunction based inverted OPV devices using current density-voltage (J-V) characteristics, space charge limited current (SCLC) measurements, capacitance-voltage (C-V) characteristics, and impedance spectroscopy (IS). OPV devices in inverted architecture, ITO/ZnO/PDPP-TNT:PC71BM/MoO{sub 3}/Ag, are processed and characterized at room conditions. The power conversion efficiency (PCE) of these devices are measured ∼3.8%, with reasonably good fill-factor 54.6%. The analysis of impedance spectra exhibits electron’s mobility ∼2 × 10{sup −3} cm{sup 2}V{sup −1}s{sup −1}, and lifetime in the range of 0.03-0.23 ms. SCLC measurements give hole mobility of 1.12 × 10{sup −5} cm{sup 2}V{sup −1}s{sup −1}, and electron mobility of 8.7 × 10{sup −4} cm{sup 2}V{sup −1}s{sup −1}.

  5. Light-triggered assembly-disassembly of an ordered donor-acceptor π-stack using a photoresponsive dimethyldihydropyrene π-switch.

    PubMed

    Krishna, V Siva Rama; Samanta, Mousumi; Pal, Suman; Anurag, N P; Bandyopadhyay, Subhajit

    2016-06-28

    Self-organization of donor and acceptor π-systems forms alternate D-A stacks of the donor and acceptor molecules. Using a photochromic π-switch as a donor and an electron deficient acceptor dye such stacks were formed. Photomodulation of the donor unit with visible light led to a photoisomerized state having a non-planar structure with reduced donor ability, thereby causing destruction of the alternate D-A π-stacks. The formation and destruction of the stacks were studied by various spectroscopy methods. Both the stacks and the depleted stacks were studied by DLS and SEM experiments. The regeneration of the stacks occurred in solution with the reversal of the photoisomerization process with ultraviolet light. Computational and differential scanning calorimetric studies validated the thermodynamics of the formation of the stacks. This work presents a reversible assembly-disassembly of a donor-acceptor π system devoid of additional auxiliary non-covalent bonding motifs in the donor and acceptor molecules. PMID:26899505

  6. Controlled energy transfer between isolated donor-acceptor molecules intercalated in thermally self-ensemble two-dimensional hydrogen bonding cages

    NASA Astrophysics Data System (ADS)

    Al Attar, Hameed A.; Monkman, Andrew P.

    2012-12-01

    Thermally assembled hydrogen bonding cages which are neither size nor guest specific have been developed using a poly (vinyl alcohol) (PVA) host. A water-soluble conjugated polymer poly(2,5-bis(3-sulfonatopropoxy)-1,4-phenylene, disodium salt-alt-1,4-phenylene) (PPP-OPSO3) as a donor and tris(2,2-bipyridyl)- ruthenium(II) [Ru(bpy)32+] as an acceptor have been isolated and trapped in such a PVA matrix network. This is a unique system that shows negligible exciton diffusion and the donor and acceptor predominantly interact by a direct single step excitation transfer process (DSSET). Singlet and triplet exciton quenching have been studied. Time-resolved fluorescence lifetime measurement at different acceptor concentrations has enabled us to determine the dimensionality of the energy-transfer process within the PVA scaffold. Our results reveal that the PVA hydrogen bonding network effectively isolates the donor-acceptor molecules in a two-dimensional layer structure (lamella) leading to the condition where a precise control of the energy and charge transfer is possible.

  7. The Dependence of Donor:Acceptor Ratio on the Photovoltaic Performances of Blended poly (3-octylthiophene-2,5-diyl) and (6,6)-phenyl C{sub 71} butyric acid methyl ester Bulk Heterojunction Organic Solar Cells

    SciTech Connect

    Fauzia, Vivi; Umar, Akrajas Ali; Salleh, Muhamad Mat; Yahya, Muhammad

    2010-10-24

    Bulk heterojunction organic solar cells using blended poly (3-octylthiophene-2,5-diyl)(P3OT) and (6,6)-phenyl C{sub 71} butyric acid methyl ester (PC{sub 71}BM) have been fabricated. P3OT and PC{sub 71}BM were used as the electron donor (D) and acceptor (A), respectively. Both materials were mixed and dissolved in dichlorobenzene with three different D:A ratios i.e. 1:3, 1:1 and 3:1 (weight) while maintained at the concentration of 2 wt%(26 mg/ml). The blended thin films were sandwiched between the indium tin oxide (ITO) coated glass and the aluminum film. This paper reports the influence of donor:acceptor ratio on the performance of solar cell devices measured by current-voltage measurement both in the dark and under 1.5 AM solar illumination. It was found that all devices showed the photovoltaic effect with poor diode behavior and the donor:acceptor ratio significantly influenced on the performance of bulk heterojunction organic solar cells.

  8. The Dependence of Donor:Acceptor Ratio on the Photovoltaic Performances of Blended poly (3-octylthiophene-2,5-diyl) and (6,6)-phenyl C71 butyric acid methyl ester Bulk Heterojunction Organic Solar Cells

    NASA Astrophysics Data System (ADS)

    Fauzia, Vivi; Umar, Akrajas Ali; Salleh, Muhamad Mat; Yahya, Muhammad

    2010-10-01

    Bulk heterojunction organic solar cells using blended poly (3-octylthiophene-2,5-diyl)(P3OT) and (6,6)-phenyl C71 butyric acid methyl ester (PC71BM) have been fabricated. P3OT and PC71BM were used as the electron donor (D) and acceptor (A), respectively. Both materials were mixed and dissolved in dichlorobenzene with three different D:A ratios i.e. 1:3, 1:1 and 3:1 (weight) while maintained at the concentration of 2 wt% (26 mg/ml). The blended thin films were sandwiched between the indium tin oxide (ITO) coated glass and the aluminum film. This paper reports the influence of donor:acceptor ratio on the performance of solar cell devices measured by current-voltage measurement both in the dark and under 1.5 AM solar illumination. It was found that all devices showed the photovoltaic effect with poor diode behavior and the donor:acceptor ratio significantly influenced on the performance of bulk heterojunction organic solar cells.

  9. Uniaxially oriented polycrystalline thin films and air-stable n-type transistors based on donor-acceptor semiconductor (diC8BTBT)(FnTCNQ) [n = 0, 2, 4

    NASA Astrophysics Data System (ADS)

    Shibata, Yosei; Tsutsumi, Jun'ya; Matsuoka, Satoshi; Matsubara, Koji; Yoshida, Yuji; Chikamatsu, Masayuki; Hasegawa, Tatsuo

    2015-04-01

    We report the fabrication of high quality thin films for semiconducting organic donor-acceptor charge-transfer (CT) compounds, (diC8BTBT)(FnTCNQ) (diC8BTBT = 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene and FnTCNQ [n = 0,2,4] = fluorinated derivatives of 7,7,8,8,-tetracyanoquinodimethane), which have a high degree of layered crystallinity. Single-phase and uniaxially oriented polycrystalline thin films of the compounds were obtained by co-evaporation of the component donor and acceptor molecules. Organic thin-film transistors (OTFTs) fabricated with the compound films exhibited n-type field-effect characteristics, showing a mobility of 6.9 × 10-2 cm2/V s, an on/off ratio of 106, a sub-threshold swing of 0.8 V/dec, and an excellent stability in air. We discuss the suitability of strong intermolecular donor-acceptor interaction and the narrow CT gap nature in compounds for stable n-type OTFT operation.

  10. Donor-acceptor pair recombination luminescence from monoclinic Cu{sub 2}SnS{sub 3} thin film

    SciTech Connect

    Aihara, Naoya; Tanaka, Kunihiko Uchiki, Hisao; Kanai, Ayaka; Araki, Hideaki

    2015-07-20

    The defect levels in Cu{sub 2}SnS{sub 3} (CTS) were investigated using photoluminescence (PL) spectroscopy. A CTS thin film was prepared on a soda-lime glass/molybdenum substrate by thermal co-evaporation and sulfurization. The crystal structure was determined to be monoclinic, and the compositional ratios of Cu/Sn and S/Metal were determined to be 1.8 and 1.2, respectively. The photon energy of the PL spectra observed from the CTS thin film was lower than that previously reported. All fitted PL peaks were associated with defect related luminescence. The PL peaks observed at 0.843 and 0.867 eV were assigned to donor-acceptor pair recombination luminescence, the thermal activation energies of which were determined to be 22.9 and 24.8 meV, respectively.

  11. Donor-Acceptor-Donor Thienopyrazines via Pd-Catalyzed C-H Activation as NIR Fluorescent Materials.

    PubMed

    McNamara, Louis E; Liyanage, Nalaka; Peddapuram, Adithya; Murphy, J Scott; Delcamp, Jared H; Hammer, Nathan I

    2016-01-01

    A series of thienopyrazine-based donor-acceptor-donor (D-A-D) near-infrared (NIR) fluorescent compounds were synthesized through a rapid, palladium-catalyzed C-H activation route. The dyes were studied through computational analysis, electrochemical properties analysis, and characterization of their photophysical properties. Large Stokes shifts of approximately 175 nm were observed, which led to near-infrared emission. Computational evaluation shows that the origin of this large Stokes shift is a significant molecular reorganization particularly about the D-A bond. The series exhibits quantum yields of up to φ = >4%, with emission maxima ranging from 725 to 820 nm. The emission is strong in solution, in thin films, and also in isolation at the single-molecule level. Their stable emission at the single-molecule level makes these compounds good candidates for single-molecule photon sources in the near-infrared. PMID:26599501

  12. Self-Enhanced Ultrasensitive Photoelectrochemical Biosensor Based on Nanocapsule Packaging Both Donor-Acceptor-Type Photoactive Material and Its Sensitizer.

    PubMed

    Zheng, Ying-Ning; Liang, Wen-Bin; Xiong, Cheng-Yi; Yuan, Ya-Li; Chai, Ya-Qin; Yuan, Ruo

    2016-09-01

    In this work, a self-enhanced ultrasensitive photoelectrochemical (PEC) biosensor was established based on a functionalized nanocapsule packaging both donor-acceptor-type photoactive material and its sensitizer. The functionalized nanocapsule with self-enhanced PEC responses was achieved first by packaging both the donor-acceptor-type photoactive material (poly{4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl}, PTB7-Th) and its sensitizer (nano-C60, fullerene) in poly(ethylene glycol) (PEG) to form a nanocapsule, which significantly enhanced PEC signal and stability of the PEC biosensor. Moreover, a quadratic enzymes-assisted target recycling amplification strategy was introduced to the system for ultrasensitive determination. Compared with other established PEC biosensors, our proposed self-enhanced approach showed higher effectivity, accuracy, sensitivity, and convenience without any addition of coreactant or sensitizers into the testing electrolyte for photocurrent amplification and performed excellent analytical properties for microRNA estimation down to femtomole level with microRNA-141 as a model. Additionally, the proposed PEC biosensor was employed for estimation of microRNA in different cancer cells and pharmacodynamic evaluation in cancer cells. This self-enhanced PEC strategy has laid the foundation for fabrication of simple, effective, and ultrasensitive PEC diagnostic devices, leading to the possibility for early diagnosis, timely stage estimation, and accurate prognosis judgment of disease. PMID:27513736

  13. Mixed donor-acceptor charge-transfer stacks formed via hierarchical self-assembly of a non-covalent amphiphilic foldamer.

    PubMed

    Jalani, Krishnendu; Kumar, Mohit; George, Subi J

    2013-06-01

    A non-covalent, amphiphilic foldamer design leads to an efficient charge-transfer complex between dipyrene (donor) and naphthalene diimide (acceptor) derivatives, which further self-assembles into one-dimensional nanofibers with an alternate (mixed) donor-acceptor arrangement. PMID:23628867

  14. The interplay of thermally activated delayed fluorescence (TADF) and room temperature organic phosphorescence in sterically-constrained donor-acceptor charge-transfer molecules.

    PubMed

    Ward, Jonathan S; Nobuyasu, Roberto S; Batsanov, Andrei S; Data, Przemyslaw; Monkman, Andrew P; Dias, Fernando B; Bryce, Martin R

    2016-02-11

    A series of phenothiazine-dibenzothiophene-S,S-dioxide charge-transfer molecules have been synthesized. Increasing steric restriction around the donor-acceptor bond significantly alters contributions from TADF and phosphorescence. Bulky substituents on the 1-(and 9) position(s) of the phenothiazine result in no TADF in the solid state; instead strong phosphorescence is observed at ambient temperature. PMID:26750426

  15. Calculation of electron transfer in ruthenium-modified derivatives of cytochrome b562

    NASA Astrophysics Data System (ADS)

    Glukhova, O. E.; Prytkova, T. R.; Shunaev, V. V.

    2016-03-01

    Quantitative theoretical studies of long-range electron transfer are still quite rare and require further development of computational methods for the analysis of such reactions. We considered the electron transfer reaction in rutenium-modified derivatives of cytochrome b562 with advanced modeling techniques. We conducted a series of ab initio calculations of the donor/acceptor interaction in protein fragments and compared the calculated electron velocity with available experimental data. Our approach takes into account the co-factor of the electronic structure and the impact of the solution on a donor-acceptor interaction. This allows us to predict the absolute values of the electron transfer rate unlike other computational methods which provide only qualitative results. Our estimates with good accuracy repeat the experimental values of electron transfer rate. It was found that the electron transfer in certain derivatives of cytochrome b562 is mainly caused by "shortcut" conformations in which the donor/acceptor interactions are mediated by the interaction of Ru-unbound ligands with groups of the protein surface. We argue that a quantitative theoretical analysis is essential for detailed understanding of electron transfer in proteins and mechanisms of biological redox reactions.

  16. Unified electronic charge transport model for organic solar cells

    NASA Astrophysics Data System (ADS)

    Mottaghian, Seyyed Sadegh; Biesecker, Matt; Bayat, Khadijeh; Farrokh Baroughi, Mahdi

    2013-07-01

    This paper provides a comprehensive modeling approach for simulation of electronic charge transport in excitonic solar cells with organic and organic/inorganic structures. Interaction of energy carrying particles (electrons, holes, singlet excitons, and triplet excitons) with each other and their transformation in the bulk of the donor and acceptor media as well as the donor/acceptor interfaces are incorporated in form of coupling matrices into the continuity equations and interface boundary conditions. As a case study, the model is applied to simulate an organic bilayer photovoltaic (PV) device to quantify the effects of photo generation, recombination coefficient, carrier mobility, and electrode work function on its PV characteristics. The study proves that electron-hole recombination at the donor/acceptor interface is the dominant mechanism that limits open circuit voltage of the device.

  17. Frontier orbital symmetry control of intermolecular electron transfer

    SciTech Connect

    Stevens, B.

    1991-09-01

    This report contains sections describing the selection of electron donor-acceptor systems, the synthesis and photophysical properties of linked electron-donor-acceptor systems, the estimation of photoinduced charge-separation rate constants from fluorescence quenching data, and radical ion-pair recombination by picosecond transient absorption spectroscopy. 9 refs., 1 fig., 7 tabs.

  18. An Obvious Improvement in the Performance of Ternary Organic Solar Cells with "Guest" Donor Present at the "Host" Donor/Acceptor Interface.

    PubMed

    Bi, Peng-Qing; Wu, Bo; Zheng, Fei; Xu, Wei-Long; Yang, Xiao-Yu; Feng, Lin; Zhu, Furong; Hao, Xiao-Tao

    2016-09-01

    A small-molecule material, 7,7-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophen]-5-yl)benzo-[c] [1,2,5]thiadiazole) (p-DTS(FBTTH2)2), was used to modify the morphology and electron-transport properties of the polymer blend of poly(3-hexythiophene) (P3HT) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) bulk heterojunctions. As a result, a 24% increase in the power-conversion efficiency (PCE) of the p-DTS(FBTTH2)2:P3HT:PC71BM ternary organic solar cells (OSCs) is obtained. The improvement in the performance of OSCs is attributed to the constructive energy cascade path in the ternary system that benefits an efficient Förster resonance energy/charge transfer process between P3HT and p-DTS(FBTTH2)2, thereby improving photocurrent generation. It is shown that p-DTS(FBTTH2)2 molecules engage themselves at the P3HT/PC71BM interface. A combination of absorption enhancement, efficient energy transfer process, and ordered nanomorphology in the ternary system favors exciton dissociation and charge transportation in the polymer bulk heterojunction. The finding of this work reveals that distribution of the appropriate "guest" donor at the "host" donor/acceptor interface is an effective approach for attaining high-performance OSCs. PMID:27525544

  19. Modulation of Intracellular Quantum Dot to Fluorescent Protein Förster Resonance Energy Transfer via Customized Ligands and Spatial Control of Donor-Acceptor Assembly.

    PubMed

    Field, Lauren D; Walper, Scott A; Susumu, Kimihiro; Oh, Eunkeu; Medintz, Igor L; Delehanty, James B

    2015-01-01

    Understanding how to controllably modulate the efficiency of energy transfer in Förster resonance energy transfer (FRET)-based assemblies is critical to their implementation as sensing modalities. This is particularly true for sensing assemblies that are to be used as the basis for real time intracellular sensing of intracellular processes and events. We use a quantum dot (QD) donor -mCherry acceptor platform that is engineered to self-assemble in situ wherein the protein acceptor is expressed via transient transfection and the QD donor is microinjected into the cell. QD-protein assembly is driven by metal-affinity interactions where a terminal polyhistidine tag on the protein binds to the QD surface. Using this system, we show the ability to modulate the efficiency of the donor-acceptor energy transfer process by controllably altering either the ligand coating on the QD surface or the precise location where the QD-protein assembly process occurs. Intracellularly, a short, zwitterionic ligand mediates more efficient FRET relative to longer ligand species that are based on the solubilizing polymer, poly(ethylene glycol). We further show that a greater FRET efficiency is achieved when the QD-protein assembly occurs free in the cytosol compared to when the mCherry acceptor is expressed tethered to the inner leaflet of the plasma membrane. In the latter case, the lower FRET efficiency is likely attributable to a lower expression level of the mCherry acceptor at the membrane combined with steric hindrance. Our work points to some of the design considerations that one must be mindful of when developing FRET-based sensing schemes for use in intracellular sensing. PMID:26690153

  20. Charge separation and photovoltaic conversion in polymer composites with internal donor/acceptor heterojunctions

    SciTech Connect

    Yu, G.; Heeger, A.J.

    1995-10-01

    The photosensitivity of semiconducting polymers can be enhanced by blending donor and acceptor polymers to optimize photoinduced charge separation. We describe a novel phase-separated polymer blend (composite) made with poly[2-methoxy-5-(2{prime}-ethyl-hexyloxy)-1,4-phenylene vinylene], MEH-PPV, as donor and cyano-PPV, CN-PPV, as acceptor. The photoluminescence and electroluminescence of both component polymers are quenched in the blend, indicative of rapid and efficient separation of photogenerated electron-hole pairs with electrons on the acceptor and holes on the donor. Diodes made with such a composite semiconducting polymer as the photosensitive medium show promising photovoltaic characteristics with carrier collection efficiency of 5% electrons/photon and energy conversion efficiency of 0.9%, {similar_to}20 times larger than in diodes made with pure MEH-PPV and {similar_to}100 times larger than in diodes made with CN-PPV. The photosensitivity and the quantum yield increase with reverse bias voltage, to 0.3 A/W and 80% electrons/photon respectively at {minus}10 V, comparable to results obtained from photodiodes made with inorganic semiconductors. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  1. Roles of Energy/Charge Cascades and Intermixed Layers at Donor/Acceptor Interfaces in Organic Solar Cells

    PubMed Central

    Nakano, Kyohei; Suzuki, Kaori; Chen, Yujiao; Tajima, Keisuke

    2016-01-01

    The secret to the success of mixed bulk heterojunctions (BHJs) in yielding highly efficient organic solar cells (OSCs) could reside in the molecular structures at their donor/acceptor (D/A) interfaces. In this study, we aimed to determine the effects of energy and charge cascade structures at the interfaces by using well-defined planar heterojunctions (PHJs) as a model system. The results showed that (1) the charge cascade structure enhanced VOC because it shuts down the recombination pathway through charge transfer (CT) state with a low energy, (2) the charge cascade layer having a wider energy gap than the bulk material decreased JSC because the diffusion of the excitons from the bulk to D/A interface was blocked; the energy of the cascade layers must be appropriately arranged for both the charges and the excitons, and (3) molecular intermixing in the cascade layer opened the recombination path through the low-energy CT state and decreased VOC. Based on these findings, we propose improved structures for D/A interfaces in BHJs. PMID:27404948

  2. Roles of Energy/Charge Cascades and Intermixed Layers at Donor/Acceptor Interfaces in Organic Solar Cells

    NASA Astrophysics Data System (ADS)

    Nakano, Kyohei; Suzuki, Kaori; Chen, Yujiao; Tajima, Keisuke

    2016-07-01

    The secret to the success of mixed bulk heterojunctions (BHJs) in yielding highly efficient organic solar cells (OSCs) could reside in the molecular structures at their donor/acceptor (D/A) interfaces. In this study, we aimed to determine the effects of energy and charge cascade structures at the interfaces by using well-defined planar heterojunctions (PHJs) as a model system. The results showed that (1) the charge cascade structure enhanced VOC because it shuts down the recombination pathway through charge transfer (CT) state with a low energy, (2) the charge cascade layer having a wider energy gap than the bulk material decreased JSC because the diffusion of the excitons from the bulk to D/A interface was blocked; the energy of the cascade layers must be appropriately arranged for both the charges and the excitons, and (3) molecular intermixing in the cascade layer opened the recombination path through the low-energy CT state and decreased VOC. Based on these findings, we propose improved structures for D/A interfaces in BHJs.

  3. Roles of Energy/Charge Cascades and Intermixed Layers at Donor/Acceptor Interfaces in Organic Solar Cells.

    PubMed

    Nakano, Kyohei; Suzuki, Kaori; Chen, Yujiao; Tajima, Keisuke

    2016-01-01

    The secret to the success of mixed bulk heterojunctions (BHJs) in yielding highly efficient organic solar cells (OSCs) could reside in the molecular structures at their donor/acceptor (D/A) interfaces. In this study, we aimed to determine the effects of energy and charge cascade structures at the interfaces by using well-defined planar heterojunctions (PHJs) as a model system. The results showed that (1) the charge cascade structure enhanced VOC because it shuts down the recombination pathway through charge transfer (CT) state with a low energy, (2) the charge cascade layer having a wider energy gap than the bulk material decreased JSC because the diffusion of the excitons from the bulk to D/A interface was blocked; the energy of the cascade layers must be appropriately arranged for both the charges and the excitons, and (3) molecular intermixing in the cascade layer opened the recombination path through the low-energy CT state and decreased VOC. Based on these findings, we propose improved structures for D/A interfaces in BHJs. PMID:27404948

  4. Optoelectronic properties and charge transfer in donor-acceptor all-conjugated diblock copolymers.

    SciTech Connect

    Botiz, I.; Schaller, R. D.; Verduzco, R.; Darling, S. B.

    2011-05-12

    All-conjugated block copolymers, which can self-assemble into well-ordered morphologies, provide exciting opportunities to rationally design and control the nanoscale organization of electron-donor and electron-acceptor moieties in optoelectronic active layers. Here we report on the steady-state and time-resolved optical characterization of block copolymer films and solutions containing poly(3-hexylthiophene) as the donor block and poly(9,9-dioctylfluorene) with and without copolymerization with benzothiadiazole as the acceptor block. Transient absorption measurements suggest rapid charge transfer occurs in both systems, with higher efficiency observed in the latter composition. These results indicate that this class of materials has promise in preparing highly ordered bulk heterojunction all-polymer organic photovoltaic devices.

  5. Light-Induced Charge Separation in Densely Packed Donor-Acceptor Coordination Cages.

    PubMed

    Frank, Marina; Ahrens, Jennifer; Bejenke, Isabel; Krick, Marcel; Schwarzer, Dirk; Clever, Guido H

    2016-07-01

    Photon-powered charge separation is achieved in a supramolecular architecture based on the dense packing of functional building blocks. Therefore, self-assembled dimers of interpenetrated coordination cages consisting of redoxactive chromophors were synthesized in a single assembly step starting from easily accessible ligands and Pd(II) cations. Two backbones consisting of electron rich phenothiazine (PTZ) and electron deficient anthraquinone (ANQ) were used to assemble either homo-octameric or mixed-ligand double cages. The electrochemical and spectroscopic properties of the pure cages, mixtures of donor and acceptor cages and the mixed-ligand cages were compared by steady-state UV-vis and transient absorption spectroscopy, supported by cyclic voltammetry and spectroelectrochemistry. Only the mixed-ligand cages, allowing close intra-assembly communication between the donors and acceptors, showed the evolution of characteristic PTZ radical cation and ANQ radical anion features upon excitation in the transient spectra. In contrast, excitation of the mixtures of the homo-octameric donor and acceptor cages in solution did not lead to any signs of electron transfer. Densely packed photo- and redox-functional self-assemblies promise molecular-level control over the morphology of the charge separation layer in future photovoltaic applications. PMID:27258549

  6. Organic Thin-Film Solar Cells Based on Donor-Acceptor Interpenetrating Nano-Interface

    SciTech Connect

    Fujii, Akihiko; Hori, Tetsuro; Moritou, Hiroki; Fukuoka, Naoki; Sakamoto, Junki; Ozaki, Masanori

    2010-12-23

    Photovoltaic cells with interpenetrating interfaces between a conducting polymer layer and a fullerene layer fabricated by a solvent corrosion method have been investigated. Using a weakly dissoluble combination of a solvent and an underlayer film, we fabricated a ''semi-layered'' structure that was maintaining a bilayer structure and furthermore interpenetrating at the interface of the conducting polymer and the fullerene layers. In these cells, high external quantum efficiencies (EQE) were obtained. The photovoltaic properties have been interpreted by the effective absorption of incident photons around the interface of conducting polymer and fullerene, the interpenetrating fullerene / conducting polymer interface involving the efficient photo-induced charge transfer, and the short distance between the electron-generation region and electrode resulting in the enhancement of the electron collection to the electrode. In these cells, both of the efficient exciton dissociations at the interpenetrating interface and the efficient carrier transports by each continuous pathway for electrons between fullerene molecules and for holes between conducting polymers occur.

  7. Organic Thin-Film Solar Cells Based on Donor-Acceptor Interpenetrating Nano-Interface

    NASA Astrophysics Data System (ADS)

    Fujii, Akihiko; Hori, Tetsuro; Moritou, Hiroki; Fukuoka, Naoki; Sakamoto, Junki; Ozaki, Masanori

    2010-12-01

    Photovoltaic cells with interpenetrating interfaces between a conducting polymer layer and a fullerene layer fabricated by a solvent corrosion method have been investigated. Using a weakly dissoluble combination of a solvent and an underlayer film, we fabricated a "semi-layered" structure that was maintaining a bilayer structure and furthermore interpenetrating at the interface of the conducting polymer and the fullerene layers. In these cells, high external quantum efficiencies (EQE) were obtained. The photovoltaic properties have been interpreted by the effective absorption of incident photons around the interface of conducting polymer and fullerene, the interpenetrating fullerene / conducting polymer interface involving the efficient photo-induced charge transfer, and the short distance between the electron-generation region and electrode resulting in the enhancement of the electron collection to the electrode. In these cells, both of the efficient exciton dissociations at the interpenetrating interface and the efficient carrier transports by each continuous pathway for electrons between fullerene molecules and for holes between conducting polymers occur.

  8. Structures and photoelectric properties of five benzotrithiophene isomers-based donor-acceptor copolymers

    NASA Astrophysics Data System (ADS)

    Cheng, Na; Ma, Yuchen; Liu, Yongjun; Zhang, Changqiao; Liu, Chengbu

    2016-04-01

    In this paper, we have investigated the structures, electronic and optical properties of five conjugated copolymers (BTT1-BTz, BTT2-BTz, BTT3-BTz, BTT4-BTz and BTT5-BTz) featuring benzotrithiophene (BTT) isomers as donor units and benzothiadiazole (BTz) as acceptor units, linked through thiophene spacers, employing many-body perturbation theory (MBPT). We have explored the isomer effects by configuration of the sulfur atoms in BTT units, aimed to get insight into how the structural modifications to the conjugated backbone can influence the molecular structures and electronic properties of conjugated polymers. Using the trimer as the computational model, the calculated low and high energy absorption bands (660 and 413 nm) for BTT1-BTz agree well with the experimental ones (645 and 430 nm) with a small offset of ~ 15 nm. On the basis of our calculations, it is found that the backbones of these polymers display different coplanarities, with the dihedral angles between the two neighboring rings varying from 12.3° to 79.0°. Importantly, both BTT1-BTz and BTT2-BTz exhibit intense adsorption around 660 and 623 nm, indicating their promising application in solar cells, whereas BTT3-BTz and BTT4-BTz display the intense adsorption at 569 and 551 nm, which are also usable in the tandem solar cells. BTT5-BTz has narrow and weak adsorption in the visible and infrared region, implying it is not conducive to the sunlight absorption. The blue shift of about 150 nm from BTT1-BTz to BTT5-BTz is suggested to be originated from the shorter effective conjugation lengths.

  9. Structures and photoelectric properties of five benzotrithiophene isomers-based donor-acceptor copolymers.

    PubMed

    Cheng, Na; Ma, Yuchen; Liu, Yongjun; Zhang, Changqiao; Liu, Chengbu

    2016-04-15

    In this paper, we have investigated the structures, electronic and optical properties of five conjugated copolymers (BTT1-BTz, BTT2-BTz, BTT3-BTz, BTT4-BTz and BTT5-BTz) featuring benzotrithiophene (BTT) isomers as donor units and benzothiadiazole (BTz) as acceptor units, linked through thiophene spacers, employing many-body perturbation theory (MBPT). We have explored the isomer effects by configuration of the sulfur atoms in BTT units, aimed to get insight into how the structural modifications to the conjugated backbone can influence the molecular structures and electronic properties of conjugated polymers. Using the trimer as the computational model, the calculated low and high energy absorption bands (660 and 413 nm) for BTT1-BTz agree well with the experimental ones (645 and 430 nm) with a small offset of ~15 nm. On the basis of our calculations, it is found that the backbones of these polymers display different coplanarities, with the dihedral angles between the two neighboring rings varying from 12.3° to 79.0°. Importantly, both BTT1-BTz and BTT2-BTz exhibit intense adsorption around 660 and 623 nm, indicating their promising application in solar cells, whereas BTT3-BTz and BTT4-BTz display the intense adsorption at 569 and 551 nm, which are also usable in the tandem solar cells. BTT5-BTz has narrow and weak adsorption in the visible and infrared region, implying it is not conducive to the sunlight absorption. The blue shift of about 150 nm from BTT1-BTz to BTT5-BTz is suggested to be originated from the shorter effective conjugation lengths. PMID:26881340

  10. Highly efficient donor-acceptor hydrazone dyes-inorganic Si/TiO₂ hybrid solar cells.

    PubMed

    Al-Sehemi, Abdullah G; Irfan, Ahmad; Al-Melfi, Mohrah Abdullah M

    2015-06-15

    We have synthesized the two donor-bridge-acceptor organic dyes (hydrazone dye 1 (HD1) and hydrazone dye 2 (HD2)) with the aim to enhance intra-molecular charge transfer then characterized by FTIR and NMR. The ground state geometries have been optimized at three different levels of theories, i.e., B3LYP/6-31G, B3LYP/6-31G and Hartee-Fock HF/6-31G. The absorption spectra and oscillator strengths in different solvents have been computed and compared with the experimental data. The vibrational spectral assignments have been performed on the recorded FTIR spectra based on the theoretical predicted wavenumbers at three different levels of theories. The effect of different solvents (CHCl3, CH3CN and C2H5OH) has been studied on the absorption wavelengths. Furthermore, we have computed the ionization potentials, electron affinities and reorganization energies of studied compounds and shed light on the charge transport properties. The hetero-junction solar cell devices were fabricated by organic-inorganic hetero-junction (Si/TiO2/dye) then the efficiency has been measured by applying the incident power 30, 50 and 70 mW/cm(2). The maximum efficiency 3.12% has been observed for HD1. PMID:25766477