abstract: The sun provides Earth with a virtually limitless source of energy capable of sustaining all of humanity's needs. Photosynthetic organisms have exploited this energy for eons. However, efficiently converting solar radiation into a readily available and easily transportable form is complex. New materials with optimized physical, electrochemical, and photophysical properties are at the forefront of organic solar energy conversion research. In the work presented herein, porphyrin and organometallic dyes with widely-varied properties were studied for solar energy applications. In one project, porphyrins and porphyrin-fullerene dyads with aniline-like features were polymerized via electrochemical methods into semiconductive thin films. These were shown to have high visible light absorption and stable physical and electrochemical properties. However, experimentation using porphyrin polymer films as both the light absorber and semiconductor in a photoelectrochemical cell showed relatively low efficiency of converting absorbed solar energy into electricity. In separate work, tetra-aryl porphyrin derivatives were examined in conjunction with wide-bandgap semiconductive oxides TiO2 and SnO2. Carboxylic acid-, phosphonic acid-, and silatrane-functionalized porphyrins were obtained or synthesized for attachment to the metal oxide species. Electrochemical, photophysical, photoelectrochemical, and surface stability studies of the porphyrins were performed for comparative purposes. The order of surface linkage stability on TiO2 in alkaline conditions, from most stable to least, was determined to be siloxane > phosphonate > carboxylate. Finally, porphyrin dimers fused via their meso and beta positions were synthesized using a chemical oxidative synthesis with a copper(II) oxidant. The molecules exhibit strong absorption in the visible and near-infrared spectral regions as well as interesting electrochemical properties suggesting possible applications in light harvesting and redox catalysis. / Dissertation/Thesis / Ph.D. Chemistry 2012

This thesis presents the synthesis and characterisation of a range of heterometallated porphyrin oligomers and other novel 3D π-conjugated porphyrin nanostructures. Subsequently, their physical organic properties were evaluated which revealed some fascinating electronic properties. Chapter 1 summarises some of the work done in the Anderson group on porphyrin nanostructures and reviews the literature regarding heterometallated porphyrin oligomers. In addition it introduces the main concepts and techniques used in the remainder of the thesis. In Chapter 2 the stabilities of a family of four linear porphyrin pentamer complexes are determined by UV-vis-NIR titrations and analysed using chemical double-mutant cycles which reveal that the binding energy of the copper centre to an axial pyridine ligand is -6.2 kJ mol^-1. Subsequently, the Zn-Zn-Cu-Zn-Zn pentamer is used in the synthesis of a heterometallated 10-porphyrin nanoring. Chapter 3 will describe the investigation of quantum interference phenomena in a bis-copper six-porphyrin nanoring by using EPR spectroscopy. We show that the exchange coupling between two spin centres is increased by a factor 4.5 in the ring structure with two parallel coupling pathways as compared to an otherwise identical system with just one coupling path. In Chapter 4 the syntheses of three isomers of the bis-copper 6-porphyrin nanoring are described. DFT calculations have indicated potential destructive interference phenomena in one of the isomers which would allow for the formation of a molecular system with behaviour resembling that of a hypothetical molecular interferometer. Chapter 5 reports on the template-directed synthesis of a π-conjugated 14-porphyrin nanoball. This bicyclic structure consists of two intersecting nanorings of 6 and 10 porphyrin units. Fluorescence up-conversion spectroscopy experiments demonstrate that electronic excitation delocalises over the whole 3D π-system within 0.3 ps if the nanoball is bound to its templates or within 5 ps if the nanoball is empty. In Chapter 6 the synthesis and characterisation of a D_4h symmetric analogue of the porphyrin nanoball is described. The structure consists of ten porphyrin units arranged as two perpendicular 6-porphyrin nanorings intersecting at two porphyrins. In the synthesis, a combination of magnesium and zinc porphyrins are used which allows for the introduction of a selective demetallation method crucial for accessing this novel structure.

Les composés polymacrocycliques présentent un grand intérêt grâce à leurs caractéristiques remarquables de coordination. Pour la première fois, l’approche synthétique fonctionnelle aux diverses composés bi- et polycycliques contenant plusieurs fragments d’éthers aza-couronnes, aux cryptands et aux supercryptands à base d’éthers aza-couronnes a été élaborée par Krakowiak et ses collaborateurs au début des années 1990, par l’usage de simples réactions de substitution nucléophile. Actuellement, les composés hétéropolymorphes polymacrocycliques, capables de former des complexes polynucléaires avec différents métaux présentent le plus grand intérêt. Dans la grande majorité des travaux la synthèse de presque toutes les composés polymacrocycliques a été réalisée à l’aide des méthodes non orthodoxes, à l’exception des molécules, composées de plusieurs macrocycles porphyriques (de la diade et de la triade), pour l’obtention desquelles ont été appliquées les réaction de Suzuki, le couplage de Sonogashira et la réaction de Heck. Le laboratoire de synthèse organominérale de la Faculté de chimie de l’Université d’Etat de Moscou a accumulé une riche expérience dans l’utilisation de l’amination pallado-catalysée pour la synthèse de diverses composés macrocycliques et polymacrocycliques, et, actuellement, on étudie activement l’arylation cupro-catalysée des di- et polyamines. À cet égard, l’étude de l’amination cupro-catalysée pour la synthèse de composés polymacrocycliques qui contiennent comme connecteurs des diamines et des polyamines a permis développer des méthodes de catalyse métallique et d’obtenir de nouveaux types de conjugués polytopiques et polymacrocycliques, qui comprennent dans leur composition structurelle des fragments éthers aza-couronnes, porphyrines et calixarènes, étudiés pour leur capacité à détecter des cations des métalliques.Le but de ces recherches est de développer des méthodes catalytiques de synthèse de conjugués polymacrocycliques qui contiennent dans leur composition structurale des fragments éthers aza-couronnes, des porphyrines et des calix[4]arènes et d’étudier leurs capacités à détecter des cations métalliques. Pour atteindre cet objectif, il est nécessaire de résoudre les problèmes suivants: 1) établir la généralité de l’amination catalysée par le Cu(I) des dérivés éthers aza-couronnes et des porphyrines contenant des halogènes et de synthétiser les dérivés aminés; 2) développer des méthodes de la macrocyclisation catalytique pour obtenir des composés macrobicycliques et macrotricycliques qui contiennent dans leur structure des fragments éthers diaza-couronnes, des tétraazamacrocycles ( cyclènes et cyclames) et des calix[4]arènes; 3) modifier les composés macrocycliques et macrobicycliques par des substituants fluorophores, y compris des porphyrines; 4) à l’aide de la spectroscopie UV et de la fluorescence, étudier la liaison cations métalliques-polymacrocycles et identifier les détecteurs potentiels moléculaires fluorescents et colorimétriques. / Polymacrocyclic compounds are of great interest due to their unique coordination properties. The first convenient synthetic approach to various polycyclic compounds containing several azacrown-ether moieties, to cryptands and supercryptands, based on azacrown-ethers, has been developed by Krakowiak and coworkers in the beginning of 1990s using simple nucleophilic substitution reactions. At present time heteropolytopic polymacrocyclic compounds, capable of forming polynuclear complexes with various metals, attract the utmost interest. In the majority of publications dealing with the synthesis of polymacrocyclic compounds non-catalytic approaches were applied, except for several porphyrin dyads and triads, which were obtained using Suzuki, Sonogashira and Heck reactions. The laboratory of organoelement compounds of Chemistry Department of Lomonosov Moscow State University has a great experience of the application of Pd-catalyzed amination reactions for the synthesis of polymacrocyclic compounds, nowadays Cu-catalyzed arylation of di- and polyamines is under investigation. Bearing it in mind we have found the research for Cu-catalyzed amination to be important in synthesis of polymacrocyclic compounds containing di- and polyamine linkers; as well as the synthesis of new types of polytopic polymacrocyclic conjugates, bearing azacrown-ether, porphyrin and calixarene moieties, by means of Pd- and Cu-catalyzed reactions; and studying their properties as metal cations detectors.The aim of the research is to develop catalytic synthetic approaches to polymacrocyclic conjugates, bearing azacrown-ether, porphyrin and calix[4]arene moieties, and to study their abilities as detectors for metal cations. For this purpose it is necessary to carry out the following investigations: 1) to study the regularities of Cu(I)-catalyzed amination of halogen derivatives of azacrown-ethers and porphyrins and to synthesize corresponding amino derivatives; 2) to develop the methods for the catalytic macrocyclization aimed at the synthesis of macrobicyclic and macrotricyclic compounds, containing diazacrown-ether, cyclen, cyclam and calix[4]arene moieties; 3) to introduce fluorophoric fragments (including porphyrins) into macrocyclic and macrobicyclic compounds; 4) to investigate metal cations binding by thus synthesized polymacrocycles using UV and fluorescent spectroscopy, and to find possible fluorescent and colorimetric detectors among them.

abstract: Wide spread adoption of photovoltaic technology is limited by cost. Developing photovoltaics based on low-cost materials and processing techniques is one strategy for reducing the cost of electricity generated by photovoltaics. With this in mind, novel porphyrin and porphyrin-fullerene electropolymers have been developed here at Arizona State University. Porphyrins are attractive for inclusion in the light absorbing layer of photovoltaics due to their high absorption coefficients (on the order of 105 cm-1) and porphyrin-fullerene dyads are attractive for use in photovoltaics due to their ability to produce ultrafast photoinduced charge separation (on the order of 10-15 s). The focus of this thesis is the characterization of the photovoltaic properties of these electropolymer films. Films formed on transparent conductive oxide (TCO) substrates were contacted using a mercury drop electrode in order to measure photocurrent spectra and current-voltage curves. Surface treatment of both the TCO substrate and the mercury drop is shown to have a dramatic effect on the photovoltaic performance of the electropolymer films. Treating the TCO substrates with chlorotrimethylsilane and the mercury drop with hexanethiol was found to produce an optimal tradeoff between photocurrent and photovoltage. Incident photon to current efficiency spectra of the films show that the dominant photocurrent generation mechanism in this system is located at the polymer-mercury interface. The optical field intensity at this interface approaches zero due to interference from the light reflected by the mercury surface. Reliance upon photocurrent generation at this interface limits the performance of this system and suggests that these polymers may be useful in solar cells which have structures optimized to take advantage of their internal optical field distributions. / Dissertation/Thesis / Ph.D. Electrical Engineering 2014

Esta dissertação apresenta a síntese, a caracterização de pentafluorofenil-piridilporfirinas base livre e substituídas com complexos de rutênio. Foi feita a investigação de como a inserção de grupos pentafluorofenil (grupos retiradores de elétrons) interfere nas das propriedades eletroquímicas, espectroscópicas e fotofísicas das porfirinas. A partir da coordenação do complexo [Ru(bpy)2Cl]+ e do cluster trinuclear de rutênio [Ru3O(Ac)6(py)2]+ à porfirina M(4-N-Py)TFPPH2 foram construídas as díades modelo [M(4-N-Py)TFFPH2{Ru3O(Ac)6(py)2}]PF6 e [M(4-N-Py)TFFPH2{Ru(bpy)2Cl}] PF6, que foram caracterizadas pelas mesmas técnicas que as porfirinas. Também foram sintetizadas as tríades assimétricas cis- e trans-[B(4-N-Py)BFFPH2{Ru3O(Ac)6(py)2} {Ru(bpy)2Cl}](PF6)2, onde há a coordenação do complexo [Ru(bpy)2Cl]+ e do cluster trinuclear de rutênio [Ru3O(Ac)6(py)2]+ aos isômeros das porfirinas cis- e trans-B(4-N-Py)BFFPH2. Estas moléculas foram caracterizadas por análise de massa ESI MS e ESI MSMS e por espectroscopia UV-Vísivel. Pelos espectros UV-Vísivel pode-se notar que os espectros são apenas uma somatória do perfil espectral dos componentes, sugerindo ausên-cia de comunicação eletrônica. No entanto estudos eletroquímicos das díades [M(4-N-Py)TFFPH2{Ru3O(Ac)6(py)2}]PF6 e [M(4-N-Py)TFFPH2{Ru(bpy)2Cl}]PF6 indicam que esta comunicação existe, embora pequena, não é negligenciável. Os estudos por análise de massa ESI MS e ESI MSMS foram realizados com as porfirinas, com o complexos [Ru(bpy)2Cl]+, com o cluster trinuclear de rutênio [Ru3O(Ac)6(py)2]+, com as díades modelos [M(4-N-Py)TFFPH2 {Ru3O(Ac)6(py)2}]PF6 e [M(4-N-Py)TFFPH2{Ru(bpy)2Cl}]PF6 e com as tríades assimétricas cis- e trans-[B(4-N-Py)BFFPH2{Ru3O(Ac)6(py)2}{Ru(bpy)2Cl}](PF6)2. As estruturas dos compostos foram confirmados por ESI MS. Para as tríades cis- e trans-[B(4-N-Py)BFFPH2 {Ru3O(Ac)6(py)2}{Ru(bpy)2Cl}](PF6)2 os experimentos ESI MSMS permitiram verificar que a fragmentação dos compostos, levam às unidades monossubstituidas [B(4-N-Py)BFFPH2{Ru3O(Ac)6(py)2}]+ e [B(4-N-Py)BPFPH2{Ru(bpy)2Cl}]+ e os fragmentos substituintes [Ru(bpy)2Cl]+ e [Ru3O(Ac)6(py)2]+. Não foi possível verificar nenhuma diferença na fragmentação dos isômeros cis- e trans- das supermoléculas. Os ensaios de luminescência mostraram que a introdução de grupos modificadores [Ru(bpy)2Cl]+ e [Ru3O(Ac)6(py)2]+ suprimem a emissão da porfirina. Os dados fotofísicos preliminares mostram que as duas unidades ligadas às porfirinas M(4-N-Py)TFPPH2, cis- e trans- B(4-N-Py)BFPPH2 estão atuando como aceptor final de carga. / This work reports the synthesis and characterization of free base pentafluorophenylpyridilporphyrins as well as the synthesis and characterization of these compounds coordinated with ruthenium complexes. We have investigated how the insertion of pentafluorophenyl groups (electronwithdrawing groups) interferes with the eletrochemical, spectroscopic and photophysical properties of the compounds. The dyads models [M(4-N-Py)TFFPH2{Ru3O(Ac)6(py)2}]PF6 and [M(4-N-Py)TFFPH2{Ru(bpy)2Cl}] PF6 were constructed using the [Ru(bpy)2Cl]+ complex, the trinuclear ruthenium cluster [Ru3O(Ac)6(py)2]+, and the free base porphyrin M(4-N-Py)TFPPH2. These dyads were characterized by the same techniques used to characterize the isolated porphyrins. The assimetric triads cis- and trans-[B(4-N-Py)BFFPH2{Ru3O(Ac)6(py)2} {Ru(bpy)2Cl}](PF6)2 were also synthesized, through coordination of the [Ru(bpy)2Cl]+ complex with the [Ru3O(Ac)6(py)2]+ trinuclear ruthenium complex and the cis- and trans isomers of the B(4-N-Py)BFFPH2 porphyrin. These molecules were characterized by ESI MS and ESI MSMS mass analyses and UV-Visible spectroscopy. The UV-Visible spectra were a sum of the spectral profile of the isolated components, suggesting a lack of eletronic communication between the units. However, electrochemical studies of the [M(4-N-Py)TFFPH2{Ru3O(Ac)6(py)2}]PF6 and [M(4-N-Py)TFFPH2{Ru(bpy)2Cl}]PF6 dyads denoted this communication exists. So, despite being low, it must not be disregarded. ESI MS and ESI MSMS mass analyses of the porphyrins, the complex [Ru(bpy)2Cl]+, the trinuclear ruthenium cluster [Ru3O(Ac)6(py)2]+, the dyads model [M(4-N-Py)TFFPH2 {Ru3O(Ac)6(py)2}]PF6, and [M(4-N-Py)TFFPH2{Ru(bpy)2Cl}]PF6 and the assimetric triads cis- and trans-[B(4-N-Py)BFFPH2{Ru3O(Ac)6(py)2}{Ru(bpy)2Cl}](PF6)2 were carried out. The structures of the compounds were confirmed by ESI MS. The ESI MSMS experiments for the cis- and trans-[B(4-N-Py)BFFPH2{Ru3O(Ac)6(py)2} {Ru(bpy)2Cl}](PF6)2 triads allow us to verify that the fragmentation of the compounds results in the monosubstituted units [B(4-N-Py)BFFPH2{Ru3O(Ac)6(py)2}]+ and [B(4-N-Py)BPFPH2{Ru(bpy)2Cl}]+, and the substituents units [Ru(bpy)2Cl]+ and [Ru3O(Ac)6(py)2]+. No difference in the fragmentation of the cis- and trans-isomers of the supermolecules was detected. The luminescence experiments showed that the porphyrin emission is almost totally quenched because of the binding of the groups [Ru(bpy)2Cl]+ and [Ru3O(Ac)6(py)2]+. Photophysics results shows that these two units bounded to porhyrins M(4-N-Py)TFPPH2, cis- and trans- B(4-N-Py)BFPPH2 act as charge receptors.

Fully conjugated porphyrin nanorings combine an end-free π-system with well defined size and shape. They provide models for testing our understanding of light harvesting in natural photosynthetic systems, and may lead to the creation of new functional materials. This thesis describes the template-directed synthesis of novel 10, 16, 18, 20, 24, 30, 40 and 50-porphyrin nanorings using small templates, as well as the investigation of their structure, electronic properties and supramolecular chemistry in solution and on surfaces. This work illustrates the scope of Vernier templating as a tool for the synthesis of monodisperse molecules of unprecedented sizes. Chapter 1 introduces key properties of porphyrins and π-conjugated linear and cyclic porphyrin oligomers and describes the principle methods of preparing non-conjugated and conjugated cyclic polymers. It also covers recent advances in the synthesis of fully-conjugated porphyrin nanorings, in particular Vernier templating. Chapter 2 discusses the formation of higher order porphyrin nanorings (18- and 24-porphyrin nanorings) in the classical synthesis of 6-porphyrin nanoring and the Vernier-templated synthesis of 12-porphyrin nanoring. Chapter 3 describes the Vernier-templated synthesis of 24-porphyrin nanoring and its characterization. Chapter 4 shows that the flexibility of 24-porphyrin nanoring can be locked by the formation of a “sandwich” complex in the presence of a bidentate ligand or by solvent-induced formation of aggregates. Chapter 5 demonstrates the use of templates to control the cyclooligomerization of linear porphyrin oligomers. Vernier-templated synthetic routes to 10-, 30- and 40-porphyrin nanorings are investigated. Chapter 6 reports the electronic properties of porphyrin nanorings as probed by electrochemistry (for 6 porphyrin nanoring) or fluorescence anisotropy measurements (for 24 porphyrin nanoring). Crystal structures of 6 and 12 porphyrin nanoring template complexes are presented. Chapter 7 contains experimental procedures and characterization data of known and novel compounds synthesized in the course of this thesis.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21594号 / 理博第4501号 / 新制||理||1646(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 依光 英樹, 教授 丸岡 啓二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

La synthèse de graphène par approche « bottom-up » fait l’objet de nombreux travaux de recherche ayant pour but de contrôler les propriétés électroniques et optiques de ce matériau par la fabrication de nanostructures avec une précision atomique. D’autre part, le contrôle de dopant dans le graphène permettant d’en moduler les propriétés suscite un grand intérêt et dans ce contexte l’utilisation de porphyrines avec un taux d’azote contrôlé est attrayante. Par leurs ressemblances structurelles, les porphyrines π-étendues peuvent être considérées comme des nanoparticules de graphène dopées à l’azote (GQDs) présentant de fortes propriétés infrarouge tandis que les briques de construction à base de porphyrines peuvent être utilisées pour la synthèse sur surface de deux type de nanoarchitectures de graphene appélées nanorubans (GNRs) et nanomèches (GNMs). Cette thèse a pour objectif de développer la synthèse de porphyrines à base d’anthracenes et de les utiliser comme précurseurs pour la fabrication de nanostructures. La première partie de cette thèse est dédiée à la synthèse organique de différentes anthracenylporphyrines et à l’étude de leurs assemblages sur surface dans la chambre d’un microscope à effet tunnel. La seconde partie est dédiée à l’étude de formation de porphyrines π-étendues via une méthode pyrolyse flash pouvant activer thermiquement des réactions de couplage par déhydrogenation entre des hydrocarbures aromatiques polyycliques (PAHs) et des porphyrines. La dernière partie est dédiée à la modification post synthétique d’une tetrabromoanthracenylporphyrine par addition de PAHs via la réaction de couplage de Suzuki-Miyaura et à la caractérisation des propriétés optiques de ces porphyrines nouvellement formées. / The synthesis of graphene via bottom-up approach is a hot topic of research that aims to control the electronic and optical properties of this material by the fabrication of atomically precised nanostructures. Moreover, the control of dopant in graphene is of great interest to modulate the properties of the material. In this context, the contribution of porphyrins with a controlled content of nitrogen is attractive in this context. Because of structural similarities with graphene quantum dots (GQDs), π-extented porphyrins can be regarded as nitrogen-doped GQD with promising NIR properties. Porphyrins are convenient building blocks for the synthesis on surface of nanoarchitectures of graphene called nitrogen-doped Graphene Nanoribbons (GNRs) and Graphene NanoMeshes (GNMs). This thesis aims to develop the synthesis of symmetrical and robust porphyrins with anthracenes and to use them as precursors for the fabrication of nanostructures. The first part of this thesis is dedicated to the organic synthesis of variety of anthracenylporphyrins and the study of their assemblies on surface in a chamber of a Scanning Tunneling Microscope. The second part is dedicated to the study of formation of π-extended porphyrins via a method of flash pyrolysis able to thermally activate dehydrogenative coupling reactions between Polycyclic Aromatic Hydrocarbons (PAHs) and porphyrins. The last part is dedicated to the post synthetic modification of a tetrabromoanthracenylporphyrin with additional PAHs via Suzuki-Miyaura coupling and the characterization of the optical properties of the resulting porphyrins.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18823号 / 理博第4081号 / 新制||理||1587(附属図書館) / 31774 / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 時任 宣博, 教授 丸岡 啓二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20387号 / 工博第4324号 / 新制||工||1670(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 松原 誠二郎, 教授 大江 浩一, 教授 中尾 佳亮 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM