A series of 28 square-planar dithiol(diimine)platinum(II) chromophoric complexes have been synthesized, characterized, and evaluated for potential efficacy in sensitization of solid state photovoltaic devices to the near-infrared regions of the electromagnetic spectrum. The effect of molecular stacking in the solid state and self-association in solution are shown to influence spectral, electronic, and magnetic properties of the chromophores. Such properties are investigated in the pure form and as partners in donor-acceptor charge transfer adducts. Finally, selected chromophores have been incorporated into single layer schottky diodes as neat films and as dopants in multi-layer organic photovoltaic devices. Evaluation of the devices internal quantum efficiency and voltage-current was measured as proof of concept.

No description available.

In donor-acceptor systems, ultrafast interfacial charge transfer (CT), charge separation (CS) and charge recombination (CR), are among the key factors in determining the overall efficiency of the optoelectronic devices. In this regime, precise knowledge of the mechanisms of these processes on the femtosecond scale is urgently required. In this dissertation, using femtosecond transient absorption and mid-Infrared spectroscopies along with steady-state absorption and emission measurements, we are not only able to address the fundamental understanding of these ultrafast dynamical processes, but also control them at various inter- and intramolecular electron donor-electron acceptor systems. In the photoinduced intermolecular charge transfer systems, where donor and acceptor are separated from each other, three systems have been investigated; cationic poly[(9,9-di(3,3′-N,N′-trimethylammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) conjugated polymer donor with 1,4-dicyanobenzene (DCB) acceptor, negatively charged porphyrin (POS) donor with positively charged (PFN) acceptor, and finally, positively charged (PFN) donor with negatively charged graphene carboxylate (GC) acceptor. Based on studying these three systems, we were able to explore some important factors and deriving forces including chemical structure, electrostatic interactions, energy band alignment, hydrogen bonding and solvents with different polarities and capabilities for hydrogen bonding that influence the rate and efficiency of the charge transfer at the interfaces of these donor-acceptor systems. For instance, unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our results reveal that the hydrogen-bonding increases the spacing between the donor and acceptor units which significantly hinders the charge-transfer process. On the other hand, in the photoinduced intramolecular charge transfer systems, where donor and acceptor are chemically attached to each other, we investigate the effects of conjugation length on photoinduced charge transfer in π-conjugated oligomers naphthalene diimide (NDI) end-capped oligo(phenylene ethynylene)s (PEn-NDI), and poly-(phenylene ethynylene) (PPE) donor backbone with (NDI) acceptor end-caps (PPE-NDI-n) systems. The results of femtosecond transient absorption and mid-IR spectroscopies show that the charge separation occurs on the 1-10 ps time scale with the rates decreasing as oligomer length increases in PEn-NDI system. In addition, in PPE-NDI-n system, the fluorescence quenching measurements indicate very efficient photoinduced electron transfer from the PPE backbone to the NDI end-groups, and the transfer efficiency increases with decreasing the number of units. Finally, the new physical insights reported in this thesis provide an understanding of several key variable components involved, thus paving the way toward the exploitation of efficient charge transfer at donor-acceptor interfaces, which is the key element and urgently required for optimal optoelectronic-device performance.

In organic photovoltaics (OPVs) the key processes relevant to device operation such as exciton dissociation and free carriers recombination occur at the donor-acceptor (D-A) interface. OPV devices require the bulk heterojunction (BHJ) architecture to function efficiently. In these BHJs, D-A interfaces are arranged in three dimensions, which makes molecular arrangements at these interfaces ill defined and hard to characterize. In addition, molecular materials used in OPVs are inherently disordered and may exhibit variable degrees of structural order in the same BHJ. Yet, D-A molecular arrangements and structure are crucial because they shape the energy landscape and photovoltaic (PV) performance in OPVs. Studies that use well-defined model systems to look in details at the interfacial molecular structure in OPVs and link it to interfacial energy landscape and device operation are critically lacking. We have used in situ photoelectron spectroscopy and ex situ x-ray scattering to study D-A interfaces in tailored bilayers and BHJs based on small molecule donors. We show preferential miscibility at the D-A interface depending on molecular conformation in zinc phthalocyanine (ZnPc)/ C60 bilayers and we derive implications for exciton dissociation. Using sexithiophene (6T), a crystalline donor, we show that the energy landscape at the D-A interface varies markedly depending on the molecular composition of the BHJ. Both the ionization energies of sexithiophene and C60 shift by over ~0.4 eV while the energy of the charge transfer state shifts by ~0.5 eV depending on composition. Such shifts create a downward energy landscape that helps interfacial excitons to overcome their binding energies. Finally, we demonstrate that when both disordered and ordered phases of D coexist at the interface, low-lying energy states form in ordered phases and significantly limit the Voc in devices. Overall our work underlines the importance of the aggregation and conformation states of molecular materials at and near the D-A interface in determining the operation and performance of OPV devices. This work shows that the role of D-A interfaces in complex BHJ devices can be unraveled through careful experimental design and by in depth characterization of planar heterojunction bilayer devices recreating model interfaces.

Molecular engineering of donor-acceptor dyads and multimodular systems to control the yield and lifetime of charge separation is one of the key goals of artificial photosynthesis for harvesting sustainably solar energy. The design of the donor-acceptor systems mimic a part of green plants and bacterial photosynthetic processes. The photochemical events in natural photosynthesis involve the capturing and funneling of solar energy by a group of well-organized chromophores referred to as an ‘antenna' system causing an electron transfer into the ‘reaction center,' where an electron transfer processes occur resulting a long-lived charge separated state. Over the last two to three decades, many efforts have been directed by the scientific community designing of multi-modular systems that are capable of capturing most of the useful sunlight and generating charge separated states of prolonged lifetimes with adequate amounts of energy. In this dissertation, we report on the design and synthesis of donor–acceptor conjugates with the goal of modulating the yield and lifetime of their charge separated states and hence, improving the conversion of light energy into chemical potential. In simple donor-acceptor systems, generally, the energy and electron transfer events originate from the singlet excited state of the donor or acceptor and can store the greatest amount of energy but must be fast to out compete intersystem crossing. To address this limitation, we have designed novel donor –acceptor conjugates that use high-energy triplet sensitizers in which electron transfer is initiated from the long lived triplet state of the donor. The triplet photosensitizers used were palladium(II) porphyrin and platinum(II) porphyrin. Heavy metal effect in these porphyrins promoted intersystem crossing and the energies of their excited state was quite high. For the case of palladium (II) porphyrin the energy stored was found to 1.89 eV and that of platinum(II) porphyrin 1.84 eV. In addition to using triplet photosensitizers as donors, we have used donors that are difficult to oxidize and hence producing long lived charge separated states with adequate amount of stored energy. The system that was used for this study is zinc porphyrin with meso-aryl pentafluorophenyl substituents and fullerene, C60 as the acceptor. The presence of fluorine substituents on zinc porphyrin makes it harder to undergo oxidation. When this high potential donor-acceptor system undergoes a photoinduced charge-separation, the estimated energy stored was found to be 1.70 eV, one of the highest reported in literature so far. To further extend the lifetime of the charge separated states generated in this high-potential zinc porphyrin-fullerene dyad a pyridine functionalized tetrathiafulvalene was axially coordinated to the Zn metal producing a supramolecular triad capable of producing long-lived charge separated state. In a subsequent study, a multi-modular donor-acceptor system composed of a porphyrin, fullerene (C60) and a BF2-chelated dipyrromethene (BODIPY) with a supramolecular arrangement in the form of porphyrin-BODIPY-C60, one of the few reported in literature. By selectively exciting BODIPY and ZnP moieties, efficient singlet-singlet energy transfer from 1BODIPY * to ZnP in toluene was observed in the case of the dyad ZnP-BODIPY. However, when ZnP is excited, electron transfer occurred with the formation ZnP.+-BODIPY-C60.- charge separated state persisting for microseconds.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第18381号 / エネ博第293号 / 新制||エネ||61(附属図書館) / 31239 / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 佐川 尚, 教授 八尾 健, 教授 萩原 理加 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM

As part of the study, photosynthetic system constructs based on BF2-chelated dipyrromethene (BODIPY), BF2-chelated azadipyrromethene (AzaBODIPY), porphyrin, phthalocyanine, oxasmaragdyrin, polythiophene, fullerene (C60), single-walled carbon nanotube and graphene are investigated. Antenna systems of BODIPY dyads and oligomers having BODIPY as an excitation energy donor connected to different acceptors including BODIPY, azaBODIPY, oxasmaragdyrin and aluminum porphyrin are studied. Different synthetic methodologies are used to afford donor-acceptor systems either directly linked with no spacer or with short spacers of varying length and orientation. The effect of donor orientation, donor optical gap as well as nature of donor-acceptor coupling on the donor-acceptor spectral overlap and hence the rate of excitation energy transfer is investigated. In all these systems, an ultrafast energy transfer followed by electron transfer is observed. In particular, in a directly connected BODIPY-azaBODIPY dyad an unusually ultrafast energy transfer (~ 150−200 f) via Förster mechanism is observed. The observation of energy transfer via Förster instead of Dexter mechanism in such closely coupled donor-acceptor systems shows the balance between spatial and electronic coupling achieved in the donor-acceptor system. Moreover, in donor-acceptor systems involving semiconducting 1D and 2D materials, covalently functionalized single-walled carbon nanotubes via charge stabilizing (TPA)3ZnP and noncovalently hybridized exfoliated graphene via polythiophene chromophores are studied for their charge transportation functions. In both cases, not only an ultrafast charge transfer in the range of (~ 2−5 p) is observed but also the charge-separated states were long lived implying the potential of these functionalized materials as efficient charge transporting substrates with organic chromophores for photovoltaic and optoelectronic applications where ultrafast intercomponent charge transfer is vital. In addition, as a final part of this dissertation, the mechanisms of electron injection and back electron transfer in heterogeneous systems involving supramolecularly anchored high potential chromophores on TiO2 film are studied by femtosecond transient absorption spectroscopy. In this study, not only are important insights gained on the utilization of supramolecular anchoring of chromophores such as porphyrins, phthalocyanines, and their perflorinated high potential analogues, chromophores currently showing promise as highly efficient sensitizers in dye sensitized solar cells, on TiO2 film but also on the effect of anchor length and sensitizer orientation on the rates of electron injection and back electron transfer at the sensitizer-TiO2 interface.

Currently, there is a great interest towards developing organic semiconductors for use in solar cells and lighting displays. Derivatives of one of the most important chromophores, diketopyrrolopyrrole (DPP), are commonly employed as the active material in field-effect transistors, as they exhibit high hole mobilities. The intramolecular structure of 2T-DPP-2T with four thiophene units(T) is classified as a donor-acceptor-donor (DAD) chromophore, where the bithiophene units are donors and the DPP unit is the acceptor. The absorption spectrum of the aggregated form of a polymer based on the 2T-DPP-2T repeat units in 1,1,2,2-tetrachloroethane solution (TCE) was measured by Janssen et. al. The spectrum is red-shifted relative to a unaggregated polymer, which is an identifying feature of a J-aggregate. In addition, the ratio of the first two vibronic peaks decreases substantially in going from the unaggregated phase to the aggregate, which is an identifying feature of an H-aggregate. These contradicting behaviors were also observed by Punzi et. al. for an aggregate of the 2T-DPP-2T chromophore. Such behavior cannot be explained by the classical Frenkel-Holstein model. One challenge has been that the intermolecular charge transfer (ICT) plays an important role in the absorption and emission spectrum in the molecular aggregates of DPP. The bulk of this thesis has been to expand the Frenkel-CT-Hosltein model to include intramolecular and intermolecular charge transfer. The model accounts unusual red-shifted H-aggregates observed in the experiments. The experimental spectra of two different DPP-based chromophores are successfully reproduced with our theoretical model. Furthermore, based on perturbative expression for ICT coupling, an effective Frenkel Holstein (EFH) model is proposed and employed to successfully simulate the absorption and emission spectrum of DPP4T aggregates, as long as charge-transfer coupling is smaller than the energy gap between the Frenkel- and ICT excitations. The emission spectrum of DPP4T is also successfully reproduced by this new model, including the temperature dependence. / Chemistry

<p dir="ltr">The intrinsic charge transfer properties of a given system are dictated by their electronic structure. The movement of electrons from electron rich to electron deficient moieties of a system can spur useful photophysical properties that have been utilized in the development of materials science. Such systems take advantage of redox-active ligands, which can actively participate in electron transfer, and have the versatility to function as either electron donors or acceptors in charge transfer processes. One of the most widely used family of ligands in the development of such materials is dithiolene (Dt), which can exists in two redox extremes; reduced ene-1,2-dithiolate(2-) (Dt^2-) and oxidized dithione (Dt⁰). Dt ligands draw inspiration from the molybdenum cofactor (Moco) found in molybdenum containing enzymes that are present in all phyla of life. The Dt^2- and Dt⁰ ligands play contrasting roles in charge transfer, however, characterization of their electronic structure when both are incorporated into a coordination complex is underexplored. Detailed computational and experimental interrogation of such complexes are presented to highlight the importance of molecular and electronic structures on their charge transfer properties. Such complexes containing a Mo core are also relevant towards the comprehension of the electronic structure of Moco. This investigation focuses on the fundamental understanding of the charger transfer properties of metallodithiolene complexes containing both Dt^2- and Dt⁰ ligands, and progress towards the synthesis of the closest Moco analogs.</p>

This dissertation research work focuses on the investigation of novel donor-acceptor systems elucidating their photochemical properties, anion binding, and their potential application in the development of artificial photosynthetic systems. The explored systems are based on oxoporphyrinogen (OxPs), porphyrins, fullerene, and boron dipyrromethene (BODIPY) based donor-acceptor systems. The photochemical properties of novel molecular systems were elucidated using UV-vis spectroscopy, fluorescence spectroscopy, electrochemical methods, computational calculations, and ultrafast transient absorption spectroscopy. A novel BODIPY-oxoporphyrinogen dyad which is able to bind with fluoride anion promoting the excited state ultrafast electron and energy transfer events mimicking the primary events in natural photosynthesis was introduced. Further, self-assembly of supramolecular complexes based on oxoporphyrinogens, fullerene, and different zinc porphyrin dimers was explored. The formed self-assembled complexes have shown photoinduced electron transfer. A novel push-pull supramolecular construct based on the spiro-locked N-heterocycle-fused zinc porphyrin was studied. The excited state charge separation and stabilization of this push-pull system was enhanced by the complexation with fluoride anion. Also, the effect of BODIPY functionalization and linkers on the electron transfer properties of a series of carbazole–BODIPY and phenothiazine-BODIPY dyads were investigated. These findings are important to develop advanced and efficient BODIPY-based donor-acceptor systems for efficient light harvesting applications. The entire study aims to expand our understanding of these systems and contribute towards the advancement of sustainable energy technologies.