The main subject of this thesis is the synthesis and investigation of the properties and potential applications of a new class of hybrid compounds consisting of a rigid, electroactive 4,4’-bipyridinium core capped by nucleobase terminal groups with hydrogen bonding abilities. A new series of small molecules consisting in a 4,4’-bipyridinium unit carrying thymine or/and adenine as capping groups was synthetized. The synthesis strategy implied the regioselective alkylation of thymine and adenine bases respectively, followed by coupling of the alkylated precursors to 4,4’-bipyridine unit via Menschutkin reaction. Electrochemical, spectroelectrochemical and optical investigations revealed an intramolecular charge transfer (CT) relationship between nucleobases as donors and 4,4’-bipyridinium unit as acceptor which is accompanied by a change in color and a shift of the reduction potentials (approx. 60 mV). The viologen-nucleobase derivatives, particularly viologens capped by thymine, were used as building blocks to create self-assembled functional nanostructures in the presence of complementary templates such as oligonucleotides or ssPNA analogues via thymine-adenine interactions. The viologen-thymine derivatives were found to partially precipitate oligonucleotides or plasmid DNA by mean of coulombic interactions and form stable polyplexes that could be used as potential gene delivery vectors. It was found that the number of positive charges, as well as the number of thymine units per viologen-thymine derivative determines whether the interaction with DNA is dominated by electrostatic or by hydrogen bonding interactions. New electroactive ionic liquid crystals were prepared by ion pairing of viologen-nucleobase dicationic species with amphiphilic 3,4,5-tris(dodecyloxy)benzene sulfonate anion. The nucleobases with ability to self-associate by hydrogen bonding were found to influence not just the thermotropic behavior, by decreasing transition temperature from crystalline to mesophase state, but also the supramolecular arrangement in solution. A versatile approach to functionalize mesoporous TiO2 film with viologen-nucleobase derivatives was developed consisting of hydrogen bonding layer-by-layer deposition of viologen-nucleobase derivatives on TiO2 surface using the thymine-adenine molecular recognition as driving force for immobilization. This method is promising and represents an easy way to construct optoelectronic device components as was demonstrated with the construction of a switchable electrochromic device.

京都大学 / 0048 / 新制・論文博士 / 博士(理学) / 乙第12887号 / 論理博第1545号 / 新制||理||1580(附属図書館) / 31641 / 京都大学大学院理学研究科 / (主査)教授 林 重彦, 教授 松本 吉泰, 教授 谷村 吉隆 / 学位規則第4条第2項該当 / Doctor of Science / Kyoto University / DGAM

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<p>The present body of work has focused on the development of the chemistry of iron complexes of macrocyclic ligands, specifically HMC and HMTI. This has proceeded along two distinct, though related, lines. First, metal-alkynyl complexes have been synthesized, and the effects of the macrocyclic ligand on the metal center – and therefore on the metal-alkynyl bond – have been extensively explored. This is first described for a mono- and bis-alkynyl pair in Chapter 2, in which the general structural and electrochemical features of the Fe(HMTI) motif are delineated. In Chapter 3, the detailed characterization of an iron HMC/HMTI family of complexes is described, which is accompanied by spectroelectrochemical (SEC) analyses and extensive DFT and TD-DFT. Finally, as described in Chapter 4, the understanding gained in the aforementioned works is leveraged to control the properties of mixed-valent complexes based on Fe(HMC/HMTI) bis-alkynyl motif, with a motivation to explore fundamental questions for the development of molecular wires.</p> <p><br></p> <p>The second realm of exploration has been concerned with understanding ferrous complexes of HMTI at a deeper level – which species have been previously reported but largely uninvestigated. Collaborative efforts have shown that these FeII(HMTI) species can have unusually long excited state lifetimes under the appropriate conditions, as discussed in Chapter 5. Further (unpublished) characterization of this family of complexes is the focus of Chapter 6, which highlights the relationship between the energy of the charge-transfer absorption band and the nature of the axial ligand.</p> <p><br></p> <p>The novel work outlined above is preceded by introductory material (Chapter 1). This chapter serves to briefly contextualize the body which follows within the landscape of the earlier established (though limited) literature on Fe(HMTI) species. Chapter 1 thus represents an attempt to illustrate the ties throughout what might otherwise (and perhaps still does) appear a disjointed conglomerate of text.</p>

There is currently a great interest to develop and market organic electronic devices, and theoretical models are needed to provide physical insight and quality predictions when designing these materials. Many organic molecules absorb in the UV-vis region of light, and therefore, UV-vis spectroscopy is a relatively simple tool that can help experimentalists "see" the packing arrangements of the molecules within each material, as long as there is a solid theoretical understanding of the photophysics that links the interactions between molecules to changes in optical features. For example, the Kasha spectral shifts have been used for decades to identify J-aggregate and H-aggregate packing arrangements from red- and blue- spectral shifts, respectively. The innate presence of vibronic coupling in organic molecules gives rise to a unique set of additional spectral signatures that are far more reliable than the Kasha spectral shifts for inferring packing arrangements. Moreover, the Kasha shifts are based entirely on Coulomb coupling between molecules, which leads to the creation of delocalized Frenkel excitons. For many π-conjugated organic molecules, however, dispersion forces in π-conjugated chromophores encourage close packing distances of about 3.5-4 Å between organic monomers, which further introduces intermolecular couplings beyond the Coulomb coupling, due to intermolecular charge transfer (CT). Therefore, much theoretical research has focused on incorporating all these effects through a Frenkel-CT-Holstein Hamiltonian, in order to better understand how different packing arrangements within a given material can be identified through specific changes in steady-state absorption and photoluminescence features. In this thesis, the Frenkel-CT-Holstein model is specifically applied to study the absorption and photoluminescent spectra of various derivatives of perylene diimide (PDI), which are of great interest as non-fullerene acceptors in organic photovoltaic design. PDIs display a plethora of packing arrangements and corresponding spectral signatures just by varying the substituents within the PDI core. This thesis first aims to understand the exciton band structure of two different PDI micro-crystals that both experience similar Frenkel-CT interference, but with one system displaying dominant Coulomb interactions while the other undergoes dominant Frenkel-CT coupling. Both are close to what is called a “null”-point, and the work in this thesis explores the photoluminescent signature as a reliable means to track which side of the “null”-point the Frenkel-CT interference lies. While the Frenkel-CT-Holstein model is successful in modeling mostly absorption spectra of aggregates composed of PDI monomers, one challenge has been that aggregates of PDIs often exhibit so-called excimer features in their photoluminescence spectra, which the model cannot account for. Systems that emit broad, structureless and red-shifted excimer peaks typically display inefficient exciton transport in organic semiconductors. The bulk of this thesis has been to expand the model to account for excimer emission, which is made possible by utilizing a Holstein-Peierls (HP) Hamiltonian that incorporates the effects of both local vibronic coupling and nonlocal Frenkel-CT coupling to intermolecular motions within a dimer. The experimental spectra for two different PDI dimer systems that display different excimer features is successfully reproduced with the new theory. This thesis concludes by analyzing how nonlocal coupling, which account for changes in the Frenkel-CT mixing along an intermolecular vibrational mode, can lead to various types of excimers. Different phase relations within the electron and hole nonlocal coupling parameters can combine with different phase relations within the electron and hole Frenkel-CT coupling parameters, leading to a rich array of excimer properties, especially when combined with the additional effects of Coulomb coupling, as well as local intermolecular vibronic coupling, which can either enhance or diminish the excimer photoluminescence. Overall, the Holstein-Peierls approach offers insight into the roles of Frenkel and CT excitons in excimer formation, and highlights the importance of the magnitude and phase of the intermolecular electron and hole transfer integrals in the ground and excited state geometries in producing distinct excimer features. The model provides further insight into the origin of excimers, which lays a foundation for future theoretical and experimental studies in designing organic materials. / Chemistry

Self-assembly of organothiols (OTs) and thiolated biomolecules onto gold nanoparticle (AuNP) surfaces remains one of the most intense areas of nanoscience research and understanding molecular interfacial phenomena is crucial. Investigation of OT adsorption onto AuNPs, including OT structure and orientation on nanoparticle surfaces, is of fundamental importance in understanding the structure and function relationship of functionalized nanoparticles. Despite the great importance of the interfacial interaction of AuNPs, the exact mechanism of OT interactions with AuNPs has remained unclear and quantitative investigation of OT adsorption has been very limited. The research reported here focused on developing a fundamental and quantitative understanding of OT interactions with AuNPs in water. In studies of OT interactions with AuNPs in water, we found that the OTs form an adsorbed monolayer on AuNPs by releasing the sulfur-bound hydrogen as a proton and acidifying the ligand binding solution. The pH measurements suggest that there is a substantial fraction (up to 45%) of the protons derived from the surface adsorbed OTs retained close to the gold surface, presumably as the counter-ion to the negatively- charged, thiolate-covered AuNPs. Charge-transfer between the surfacesorbed thiolate and the AuNPs is demonstrated by the quenching of the OT UV-vis absorption when the OTs are adsorbed onto the AuNPs. Using a combination of surface enhanced Raman spectroscopy (SERS), density function calculations, and normal Raman spectroscopy, the pH dependence of mercaptobenzimadazole (MBI) adsorption onto AuNPs was systematically studied. By using the ratiometric SERS ligand quantification technique, MBI adsorption isotherms were constructed at three different pHs (1.4, 7.9, and 12.5). The Langmuir isotherms indicate that MBI thione has a higher saturation packing density (~­631 pmol/cm2) than MBI thiolate (~­568 pmol/cm2), but its binding constant (2.14 x 106 M-1) is about five times smaller than the latter (10.12 x 106 M-1). The work described in this dissertation provides a series of new insights into AuNP-OT interaction, and structure and properties of OTs on AuNPs.

The demand for low-power A/D conversion techniques has motivated the exploration of charge-transfer amplifiers (CTAs) to construct efficient, precise voltage comparators. Despite notable advantages over classical, continuous-time architectures, little is understood about the dynamic behavior of CTAs or their utility in precision A/D converters. Accordingly, this dissertation presents several advancements related to the design and analysis of charge-transfer amplifiers for low-power data conversion. First, an analysis methodology is proposed which leads to a deterministic model of the voltage transfer function. The model is generalized to any timing scheme and can be extended to account for nonlinear threshold modulation. The model is compared with simulation results and test chip measurements, and shows good agreement over a broad range of circuit parameters. Three new charge-transfer amplifier architectures are proposed to address the limitations of existing designs: first, a truly differential CTA which improves upon the pseudo-differential configuration; second, a CTA which achieves more than 10x reduction in input capacitance with a moderate reduction in common mode range; third, a CTA which combines elements of the first two but also operates without a precharge voltage and achieves nearly rail to rail input range. Results from test chips fabricated in 0.6 um CMOS are described. Power dissipation in CTAs is considered and an idealized power consumption model is compared with measured test chip results. Four figures of merit (FOMs) are also proposed, incorporating power dissipation, active area, input charging energy and accuracy. The FOMs are used to compare the relative benefits and costs of particular charge-transfer amplifiers with respect to flash A/D converter applications. The first 10-bit CTA-based A/D converter is reported. It consumes low dynamic power of 600 uW/MSPS from a 2.1 V supply, 40% less than the current state of the art of 1 mW/MSPS. This subranging type converter incorporates capacitive interpolation to achieve a nearly ideal comparator count and power consumption. A distributed sample-and-hold (S/H) eliminates the need for a separate S/H amplifier. A test chip, fabricated in 0.6 um 2P/3M CMOS, occupies 2.7 mm2 and exhibits 8.2 effective bits at 2 MSPS.

The impact parameter (IP) approximation is a semiclassical model in quantum scattering theory wherein N large masses interact with one small mass. We study this model in one spatial dimension using the tools of time-dependent scattering theory, considering a system of two large-mass particles and one small-mass particle. We demonstrate that the model's predictive power becomes arbitrarily good as the masses of the two heavy particles are made larger by studying the S-matrix for a particular scattering channel. We also show that the IP wave functions can be made arbitrarily close to the full three-body solution, uniformly in time, provided one of the large masses is fixed in place, and that such a result probably will not hold if we allow all the masses to move. / Ph. D.

Charge transfer salts of Tetracyanoquinodimethane (TCNQ) were synthesised and their electrical and magnetic properties were investigated. These salts show unusual electrical and magnetic behaviour in contrast to conventional organic compounds. These salts have crystal structures which in general consist of TCNQ radical ions stacked in chains, isolated from each other by the diamagnetic cations. They are thus regarded as "one-dimensional" electrical and magnetic systems. The ESR spectra of these salts are attributed to triplet excitons showing that the spin-spin and electronelectron correlation effects are important. In the ESR spectra (Chapter III) of some TCNQ salts dipolar splitting is observed confirming the spin-spin interaction. These triplet excitons are regarded as bound electron-hole pairs. The experimentally determined dipolar splitting tensors are presented in Chapter III and the intensity data in Chapter IV. A large number of fine structure lines are observed in the ESR spectra of Pyridinium-TCNQ and 4-Aminopyridinium-TCNQ apart from regular triplet exciton lines (Chapter III). These lines are attributed to the trapping of excitons on an extended formula finit (TCNQ2 )n. In Chapter IV the temperature dependent magnetic susceptibilities are discussed in terms of Heisenberg antiferromagnetism and Pauli paramagnetism. In Chapter V temperature dependent behaviour of electrical conductivity is discussed in terms of an exciton band model, the lattice structure of the salts and one-dimensional lattice consisting of defects giving rise to high and low conducting segments. Low temperature electrical and magnetic phases are discussed (Chapters IV and VII) in terms of a band and hopping mechanisms.In Chapter VI self consistent field calculations are made with reference to the tight binding one electron band theory using simplified Roothaan equations considering CNDO approximations. Theoretical results are related to experimental band gaps, spinspin interactions and charge alteration.