Die vorliegende Arbeit beschäftigt sich mit der Leistungssteigerung organischer Solarzellen durch Änderung der Geometrie an der Donor-Akzeptor Grenzfläche und dem Einstellen der elektronischen Eigenschaften von Grenzflächen durch molekulares p-Dotieren. Kristalline und gleichmäßige Nanosäulen aus dem organischen Halbleiter Pentazen wurden durch glancing angle deposition (GLAD) hergestellt, die einen ineinandergreifenden Heteroübergang zu Methanofulleren [6,6]-Phenyl-C61-Butansäure Methylester (PCBM) als Akzeptor ermöglichten. Die Kurzschlussspannung der nanosäulenbasierten Solarzellen war signifikant erhöht im Vergleich zu planaren Heteroübergängen zwischen denselben Materialien. Die Leistungssteigerung der Solarzellen konnte maßgebend der vergrößerten Grenzfläche zugewiesen werden, wegen des verringerten Einflusses der kurzen Exciton Diffusionslänge. Molekulares p-Dotieren mit Tetrafluorotetracyanoquinodimethan (F4TCNQ) als Dotand in polyfuranbasierten Solarzellen wurde für verschiede Dotierkonzentrationen untersucht. Ultraviolettphotoelektronenspektroskopie wurde verwendet, um die Veränderungen der Energieniveaus mit zunehmender Dotierkonzentration zu analysieren, welche zu einer Vergrößerung der 0,2 V Kurzschlussspannung auf bis zu 0,4 V führte. Nach Kombination dieser Beobachtung mit Ergebnissen an dotierten Polymerfilmen, insbesondere bezüglich deren Morphologie und Absorptionsverhalten, wurde vorgeschlagen, dass ein resultierender Dipol an der Donor-Akzeptorgrenzfläche präsent ist. Zusammenfassend zeigt die vorliegende Arbeit das Potential sowohl der GLAD Technik als auch des molekularen, elektrischen Dotierens für die Leistungsverbesserung organischer Solarzellen. / The present work mainly focuses on improving the performance of OPVCs by tailoring the donor-acceptor interface geometry and by tuning the electrical properties of interfaces with p-type molecular doping. Crystalline and uniform nanocolumns of pentacene (PEN) and diindenoperylene (DIP) were fabricated by glancing angle deposition (GLAD), forming an interdigitated donor/acceptor heterojunction with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and/or fullerene as the electron acceptor. The short circuit current of nanocolumn-based OPVCs increased significantly compared to planar heterojunction OPVCs made from the same materials. The performance improvement of OPVCs had been verified to be contributed decisively by the donor-acceptor interface area enlargement because of reduced impact of short exciton diffusion length in organic materials. P-type molecular doping as applied in polyfuran (PF) based OPVCs was investigated by using tetrafluorotetracyanoquinodimethane (F4-TCNQ) as the dopant for various doping ratios. Ultraviolet photoelectron spectroscopy (UPS) was applied to analyze the energy level shift with increasing doping ratio leading to the enlargement of the open circuit voltage in OPVCs, from 0.2 V to close to 0.4 V. Combining this observation with the results of doped polymer films, their morphology and absorption behavior, a net dipole pointing towards the donor material at the donor-acceptor interface of OPVCs is proposed. Overall, this work demonstrates the potential of both the GLAD technique and molecular electrical doping for improving the performance of OPVCs.

Les travaux présentés dans ce mémoire de thèse portent sur la synthèse et l’étude des propriétés spectroscopiques et électrochimiques de systèmes donneur-accepteur conçus pour des applications variées telles que l’électrofluorochromisme, l’absorption à deux photons et le photovoltaïque. La s-tétrazine a été choisie comme accepteur pour sa forte affinité électronique, ses propriétés émissives remarquables et sa capacité à s’organiser via des interactions intermoléculaires de type &#61552--stacking. La triphénylamine a été sélectionnée comme donneur pour son faible potentiel d’ionisation, ses propriétés spectroscopiques (fortes absorption et émission) et la modulation facile de ses propriétés par changement de substituants. Sept dérivés de triphénylamine ont été synthétisés ainsi que dix-huit nouveaux composés multichromophoriques à base de tétrazine et de triphénylamine présentant cinq liens différents et des substituants variés. Ils ont été caractérisés par électrochimie et spectroscopie (stationnaire et résolue en temps). L’étude de la modulation de leurs propriétés photophysiques par le changement de l’état rédox a ensuite été réalisée. Dix composés présentant un lien permettant la conjugaison entre la triphénylamine et la tétrazine ont été synthétisés et caractérisés par électrochimie et spectroscopie. Compte-tenu de leurs propriétés, six d’entre eux ont été testés en absorption à deux photons et deux ont étés retenus pour être utilisés comme donneurs dans une cellule photovoltaïque organique. Par ailleurs, deux réactions ont été étudiées en détail pour expliquer la formation des produits obtenus, inattendus à un premier abord. / This work deals with the synthesis and the spectroscopic and electrochemical studies of donor-acceptor systems which have been designed for electrofluorochromism, two-photon absorption and photovoltaics. s-Tetrazine has been chosen as the acceptor for its high electron affinity, its emission properties and its ability to structure a layer thanks to intermolecular interactions (&#61552--stacking). Triphenylamine has been selected as the donor for its low ionization potential, its spectroscopic properties (high absorption and emission) and the easy modulation of its properties by changing the substituents. Seven triphenylamine derivatives have been synthesized as well as eighteen new multichromophoric compounds based on tetrazine and triphenylamine which have five different links and various substituents. They have been characterized by electrochemistry and spectroscopy (stationary and time-resolved). The study of the modulation of the photophysic properties with the controle of the redox state has been then done. Ten compounds having a conjugating link between the tetrazine and the tetrazine have been synthesized and characterized by electrochemistry and spectroscopy. Given their properties, six of them have been tested in two-photon absorption and two of them have been selected to be used as a donor in an organic solar cell. Moreover two reactions have been examined in depth in order to explain some unexpected synthesis results.

Pour la recherche de candidats d’intérêt thérapeutique, l’accès à des systèmes carbonés toujours plus complexes peut se heurter à divers problèmes synthétiques. Afin d’enrichir la diversité structurales, il est nécessaire de pallier aux difficultés synthétiques par le développement de nouveaux outils de synthèse. Dans ce contexte, ce travail s’est principalement orienté sur l’accès de cycles carbonés par des réactions d’expansion de cycle via l’utilisation de composés polarisés. Une première partie est réalisée avec l’utilisation de l’α-chlorodiazoacétate d’éthyle dans la réaction d’expansion de cycle de Tiffeneau-Demjanov pour la synthèse de céto-esters cycliques avec l’incorporation d’un centre tétrasubstitué présentant un atome de chlore. Dans un second temps, le développement d’une réaction de cycloaddition (5+3) à partir de deux entités cyclopropaniques polarisées a été mené au laboratoire. Cette méthodologie a conduit à décrire une nouvelle réactivité des composés cyclopropanes donneurs-accepteurs pour former des lactones α,β,γ-trisubstituées via une activation avec un acide de BrØnsted. Une étude approfondie par des calculs théoriques ont permis d’appréhender le mécanisme réactionnel et la sélectivité de cette transformation. La dernière partie a examinée la réactivité d’une nouvelle classe de molécule : les vinylbiscyclopropanes. Ces composés peuvent conduire à la famille des benzocyclobutènes et aux composés cycliques à 8 chainons par des réactions de réarrangement ou de transposition sigmatropique [3.3] formelle. Ce dernier motif est toujours à l’étude et devrait permettre un accès rapide à de multiples structures carbonées. / In the quest for new therapeutic candidates, the description of novel synthetic approaches to access to increasingly complex carbon systems remains a daunting challenge. In order to increase the structural of such scaffolds, it is necessary to overcome the encountered difficulties by developing new straightforward an efficient tools. In this context, this work has mainly focused on the access of structurally defined carbon cycles by ring expansion reactions via the use of polarized compounds. The first part of this study has been devoted to the Tiffeneau-Demjanov ring expansion reaction using ethyl α-chlorodiazoacetate. This approach allowed us to access highly versatile cyclic keto esters displaying a tetrasubstitued carbon center bearing a chlorine atom. The next topic of this study has been focused on the development of a (5 + 3) cycloaddition reaction between two polarized cyclopropane entities. This methodology led to the description of a novel reactivity of donor-acceptor cyclopropanes compounds to form α,β,γ-trisubstituted lactones under a BrØnsted acid activation. In order to gain mechanistic insights, a theoretical study has also been conducted which led us to rationalize the mechanism and the selectivity of this transformation. The last part described the reactivity of a underexplored class of molecule, the vinylbiscyclopropanes. These compound, can lead to the benzocyclobutene family and to the 8 membered-ring compounds through rearrangement or formal [3.3] sigmatropic rearrangement reaction. This last class of compound is still under study and should allow rapid access to diverse cyclic structures.

Philosophiae Doctor - PhD / This thesis is based on the study of electropolymerization and electrochromism of poly(4,7- dithien-2-yl-2,1,3-benzothiadiazole) (P(DTBT) and its copolymer with 3-methoxythiophene (MOT) in imidazolium ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimbf4) hydrophilic, 1-butyl-3-methylimidazolium hexafluorophosphate (bmimpf6) and 1- butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (bmimtnf2) hydrophobic ILs. Traditional organic solvents acetonitrile and dichloromethane in the presence of 0.1 M tetrabutylammonium perchlorate (n-Bu4NClO4) as a supportive electrolyte was also used as a medium for comparison. Besides, a more hydrophobic ionic liquid, 1-octyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide (octmimtnf2) was also used for the electrodeposition of poly(3-methoxythiophene) (PMOT). The techniques employed are cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), uv-visible spectroelectrochemistry and scanning electron microscopy (SEM). 4,7-Dithien-2-yl-2,1,3-benzothiadiazole (DTBT) a type of donor –acceptor monomer and 3- methoxythiophene (MOT) has been electropolymerized using ionic liquids as growth and supportive electrolytes.

Pour cette thèse, des systèmes donneur-accepteur (DA) modèles pour le photovoltaïque organique ont été étudiés par microscopie à force atomique en mode non contact (nc-AFM) et microscopie à sonde de Kelvin (KPFM). Ces systèmes DA présentent une structure et des propriétés électroniques mieux contrôlées que dans la plupart des hétérojonctions DA en volume.Afin, d'étudier les propriétés optoélectroniques d'architectures DA présentant une séparation de phase à l'échelle de la dizaine de nanomètres, il est indispensable d'optimiser la résolution des modes nc-AFM/KPFM. Dans ce travail, l'influence du régime d'interaction pointe-surface sur les mesures a été étudiée dans le cas d'auto-assemblages de P3DDT sur substrat HOPG. Nous avons ainsi démontré que l'imagerie dans le régime d'interaction à courte portée améliore non seulement la résolution latérale, mais permet également de réaliser des mesures de hauteur plus réalistes.Ensuite, un système DA à base de FG1:[70]PCBM a été étudié. Pour ce mélange DA, la nanostructure et l'échelle de la séparation de phase peuvent être ajustées grâce aux propriétés cristal liquide du composé donneur FG1. Les potentiels mesurés dans le noir sont consistants avec la morphologie attendue en surface et en volume. La relation entre le photo-potentiel de surface (SPV) et le régime d'interaction pointe-surface a pu être précisément analysée. Une résolution optimale est obtenue dans les images de SPV en travaillant près du seuil de dissipation.Enfin, une nouvelle génération de diades comprenant des groupements donneur et accepteur a été étudiée. La nature de l'auto-assemblage sur HOPG a été établie sur la base d'études comparatives de microscopie à effet tunnel et de nc-AFM, avec le support de simulations en mécanique et dynamique moléculaire. Les mesures de photo-potentiel de surface ont ensuite permis de démontrer qu'il était possible d'étudier les mécanismes de photo-génération des porteurs jusqu'à l'échelle de la mono-couche moléculaire. / During this thesis, model donor-acceptor (DA) systems for organic photovoltaics have been studied by non-contact atomic force microscopy (nc-AFM) and Kelvin probe force microscopy (KPFM). To enhance the understanding of the optoelectronic processes on the nanoscale, DA systems with better defined structural and electronic properties than the one of most bulk heterojunction blends (BHJ), have been studied.With DA phase-separations of below 10nm in organic photovoltaic systems, the highest possible resolution has to be achieved by KPFM to investigate optoelectronic processes. It has been shown that nc-AFM/KPFM measurements in the regime of short range (SR) forces can increase imaging resolution. In preparation of such investigations, the influence of the interaction regime on the topographic measurement via KPFM has been studied for a self-assembly of P3DDT on HOPG. It is demonstrated that imaging in the SR-regime not only increases the lateral resolution, but also assures a correct topographic height values.In a next step, DA blends of FG1:[70]PCMB have been studied by KPFM. For these BHJs, the structure and the scale of the DA phase-separation can be tuned via the liquid crystal behavior of the donor FG1. The in dark potential contrasts are consistent with surface and bulk morphology. The relationship between the surface photovoltage (SPV) and the tip-sample interaction regime has been analyzed. An optimal resolution for SPV imaging is obtained when measuring next to the onset of dissipation.Finally, a new generation of DA dyad with donor and acceptor moieties has been studied. Its self-assembly on HOPG has been determined via a comparative study by scanning tunneling microscopy and nc-AFM plus molecular mechanics and dynamics simulations. By KPFM the charge carrier generation and collection has been analyzed down to the level of a single molecular layer. A clear relationship between the dyads' molecular assembly and their photovoltaic properties can be established.

Dans ce travail, les copolymérisations radicalaires contrôlées de monomères donneurs (dérivés du styrène) et accepteurs (maleimides N-substitués) ont été effectuées afin de préparer des polymères à séquences contrôlées. Ces macromolécules ont été préparées par polymérisation radicalaire contrôlée par la voie des nitroxides en utilisant le SG1 comme agent de contrôle. Des polymères ayant des microstructures bien définies ont été obtenus par le contrôle du temps de l’addition d’une petite quantité de monomère accepteur au cours de la polymérisation d’un large excès de monomère de type donneur. Dans cette thèse, des nouveaux dérivés styréniques para-substitués ont été sélectionnés afin de préparer une variété de polymères fonctionnels à séquences contrôlées. Par exemple, des polyélectrolytes à base de poly(4-hydroxystyrène)s et poly(vinyl benzyle amine)s ont été obtenus par polymérisation de dérivés protégés du styrène (4-tert-butoxystyrène, 4-acetoxystyrène et N-(p-vinyl benzyl)phthalimide) avec une quantité non-stœchiométrique de maleimides N-substitués. Par ailleurs, des polymères PEGylés biocompatibles et solubles dans l’eau ont également été étudiés. Des polymères à séquences contrôlées portant des fonctions alcynes protégées sur chaque unité de styrène ont été dans un premier temps synthétisés. La suppression de ces groupes protecteurs a permis le greffage du α-méthoxy-ω-azido-PEG sur les fonctions alcynes libres en employant la chimie click de type CuAAC. Finalement, des polymères semi-cristallins à séquences contrôlées ont été élaborés en utilisant le styrène d’octadécyle comme monomère donneur. Les propriétés thermiques de ces polymères ont été étudiées afin d’évaluer l’influence de la microstructure sur le comportement de leur cristallisation. / In this work, controlled radical copolymerizations of donor (styrenic derivatives) and acceptor monomers (N-substituted maleimides, MIs) have been investigated in order to synthesize sequence-controlled polymers. These macromolecules were prepared by nitroxide mediated polymerization using the nitroxide SG1 as a control agent. Polymers with defined microstructures were obtained by time-controlled addition of small amounts of acceptor monomers during the polymerization of a large excess of donor monomer. In this thesis, new styrenic derivatives have been studied in order to design sequence-controlled polymers with functional backbones. For example, sequence-controlled polyelectrolytes based on poly(4-hydroxystyrene)s and poly(vinyl benzyl amine)s were obtained through the polymerization of protected styrenic derivatives (i.e. 4-tert-butoxystyrene, 4-acetoxystyrene and N-(p-vinyl benzyl)phthalimide) with non-stoichiometric quantities of N-substituted maleimides. Furthermore, the preparation of PEGylated biocompatible water-soluble polymers was also investigated. Sequence-controlled polymers bearing protected alkyne functional groups on each styrene units were first synthesized followed by the removal of their protecting groups allowing the grafting of α-methoxy-ω-azido-PEG on free alkyne moieties via CuAAC mediated click reaction. Finally, sequence-controlled semi-crystalline polymers were synthesized using octadecylstyrene as a donor monomer. The thermal properties of these polymers were studied to evaluate the influence of polymer microstructure on crystallization behavior.

This thesis consists of two parts and nine chapters. The first part (Part I) presents theoretical studies on non-radiative mode of excitation energy transfer (EET) in donor-acceptor (D-A) systems involving metal nanoparticles. Part I contains four chapters and describes EET in following different D-A systems: (i) dye and a spherical metal nanoparticle of different sizes, (ii) two spherical metal nanoparticles, and (iii) two prolate shaped metal nanoparticles at different relative orientations. Part II provides a detailed study on the origin of photochemical funneling of excitation energy in conjugated polymers like poly-[phenylenevinylene] (PPV) and consists of three chapters. The ninth chapter provides a concluding note. The thesis begins with a basic introduction on Forster resonance energy transfer(FRET), presented in chapter 1. This chapter provides a detail derivation of Forster’s rate expression for a non-radiative process of EET from a donor to an acceptor molecule and discusses the limitations of Forster theory. The chapter highlights the huge success of FRET technique in understanding biological processes assisted by changes in conformations of biopolymers under conditions where Frster theory is valid. The chapter also discusses practical limitations of FRET technique such as use of pre-averaged value of orientation factor and photobleaching of dye molecules. Part I starts with chapter 2 which explains the advantages of using metal nanoparticles over dye molecules in D-A systems. The chapter discusses recent experimental re-ports of excitation energy transfer to nanoparticles, now commonly referred to as nanoparticle surface energy transfer (NSET). Theories describing the process of EET from a dye molecule (dye molecule is assumed to be a point dipole) to a planar metallic surface are discussed. In the case of energy transfer from a donor dye molecule to a planar metallic surface, the distance dependence of the rate of EET is found to vary as 1/d4 where dis a distance from the center of a dye molecule to the metallic surface. This is unlike conven-tional FRET where rate of EET follows 1/R6 distance dependence with R as a distance between the centers of D and A. Also, a recent experimental study by Yun et al [J. Am. Chem. Soc. 127, 3115 (2005)] on energy transfer from a dye molecule to a spherical gold nanoparticle reports that the rate of EET follows 1/d4 distance dependence. The remaining chapters of this part focus on understanding this deviation from the Forster theory in different D-A systems. Chapter 3 describes quantized electro-hydrodynamic approach used to model the plasmonic excitations in metal nanoparticles. The optical absorption frequencies of nanoparticles computed here are subsequently used in chapters 4 and 5 for the calculation of the rate of EET. The chapter discusses the merits and de-merits of electro-hydrodynamic approach in comparison to other available techniques. The electro-hydrodynamic method of calculating the absorption frequencies provide a physically appealing, mathematically simple and numerically tractable approach to the problem and is also at the same time, semi-quantitatively reliable. The optical frequencies obtained as a function of size and aspect ratio of metal nanoparticles are found to be in good agreement with physical predictions. Chapter 4 studies the distance dependence of rate of EET for a D-A system similar to one studied by Yun et al [J. Am. Chem. Soc. 127, 3115 (2005)]. The chapter contains the relevant derivations of the quantities required for computing the interaction matrix elements. The dependence of the rate of EET on R is found surprisingly to be in agreement with Forster theory even at intermediate distances compared to the size of spherical nanoparticles (a). However, the dependence of rate of EET on d is found to vary as 1/dσwith σ=3 - 4 at intermediate distances which is in good agreement with the experimental results of Yun et al. At large values of d, the distance dependence of rate is found to vary as 1/d6 . The chapter discusses the physical basis behind these results. The theory predicts a non-trivial dependence of rate on the size of a nanoparticle which ultimately attains the asymptotic a3 size dependence. The rate of EET is also studied for different orientations of dye molecule. Chapter 5 studies surface plasmon mediated EET between two metal nanoparticles. The rate of EET between two prolate and spherical shaped silver nanoparticles is studied as a function of Rand d. d, in present chapter denotes surface-to-surface separation distance between two nanoparticles. In case of EET between two non-spherical nanoparticles, even at separations larger than the size of the nanoparticle, a significant deviation from 1/R6 dependence is obtained. However, 1/R6 distance dependence of EET rate is found to be robust for spherical nanoparticles over an entire range of separations. The deviation of rate from 1/R6 distance dependence becomes more pronounced with in-crease in the aspect ratio of the nanoparticle. The relative orientation of the nanoparticles is found to markedly influence the R-dependence of EET rate. Interestingly, the relative orientation of nanoparticles effect the d-distance dependence of the rate to a lesser extend in comparison to the R-dependence of the rate. Therefore, we predict that for non-spherical nanoparticles studying EET rate as a function of will provide more conclusive results. The chapter also discusses the size dependence of rate of EET for this particular D-A system. In Part II, excitation energy transfer (EET) in a conjugated polymer is studied. To start with, chapter 6 provides a brief introduction to photophysics of conjugated polymers. The chapter discusses the nature of photoexcitations in these systems and stresses on the influence of polymer’s morphology on the optical properties of conjugated polymers. Chapter 7 describes the theory used for modeling conjugated polymer chain. A polymer chain consists of number of spectroscopic units (chromophores) of varying lengths. The average length of chromophores in conjugated polymer depends on defect concentration. In the present study we treat an excitation generated on each chromophore within “particle-in-a-box” formalism but one that takes into account the electron-hole interactions. The transition dipole moments and the radiative rates are computed for different lengths of chromophores with parameters appropriate for PPV chain. These quantities are used in chapter 8 for calculating the absorption and emission spectra of conjugated polymer chains at different defect concentrations. The main aim of Chapter 8 is to understand the origin of photochemical funneling of excitation energy in conjugated polymers. PPV chain is modeled as a polymer with the length distribution of chromophores given either by a Gaussian or by a Poissonian distribution. We observe that the Poissonian distribution of length segments explains the optical spectra of PPV rather well than the Gaussian distribution. The Pauli’s master equation is employed to describe the excitation energy transfer among different chromophores. The rate of energy transfer is assumed to be given here, as a first approximation, by the well-known Forster expression. The observed excitation population dynamics confirm the photochemical funneling of excitation energy from shorter to longer chromophores of the polymer chain. The calculations show that even in steady state more than one type of chromophore contribute towards the emission spectrum. The observed difference between the calculated emission spectra at equilibrium and in steady state indicates the existence of local domains in a polymer chain within which the non-radiative excitation energy transfer from shorter to longer chromophores take place. These results are found to be in agreement with recent experimental reports. The concluding chapter 9 gives a brief summary of the outcome of the thesis and ends up with suggestion of a few future problems which in current scenario are of great interest.

Polyzyklische organische Moleküle und deren Derivate sind eine Klasse von Nanostrukturen, die wegen diverser möglicher Anwendungen in molekularer und organischer Elektronik viel Aufmerksamkeit in der Wissenschaft erregt haben. Um ihre einzigartigen Eigenschaften in vollem Umfang auszunutzen, muss man das Verhalten von molekularen Systemen auf der Nanoskala verstehen und eine Reihe von Herstellungsverfahren entwickeln. In dieser Arbeit werden molekulare Nanostrukturen durch den Bottom-Up-Ansatz der Oberflächensynthese erzeugt. Als Untersuchungsmethode gilt Rastertunnelmikroskopie (STM) bei tiefen Temperaturen und im Ultrahochvakuum als Werkzeug der Wahl. Drei verschiedene molekulare Systeme werden ausführlich erforscht, mit dem Ziel organische Nanostrukturen mit gewünschten Eigenschaften und atomarer Präzision zu erzeugen. Im ersten Teil dieser Arbeit wird eine Cyclodehydrierungsreaktion erfolgreich für die Synthese von asymmetrischen Starphen verwendet. Es wird dann gezeigt, dass dieses Molekül als unimolekulares NAND-Logikgatter fungieren kann. Dabei wird die Positionierungsänderung der elektronischen Resonanz nach der Zufügung einzelner Goldatome an die Inputs des Moleküls gemessen. Eine Kombination aus atomarer und molekularer Lateralmanipulation mithilfe der Spitze des Rastertunnelmikroskops sowie Rastertunnelspektroskopie wird verwendet, um dieses Verhalten zu demonstrieren. Die steuerbare Verschiebung von molekularen Resonanzen entsteht wegen der asymmetrischen Form des Starphens und wurde theoretisch vorhergesagt. Molekulare Drähte werden im zweiten Teil der Arbeit durch die oberflächenassistierte Ullmann-Kupplung hergestellt. Ihr Baustein besteht aus abwechselnden Donor- und Akzeptorgruppen und wurde speziell vorgesehen, um leitfähige flexible molekulare Drähte herzustellen. Die Leitfähigkeit wird durch Ziehen einzelner Drähten von der Oberflächen mit der STM-Spitze gemessen. Theoretische Berechnungen der komplexen Bandstruktur der molekularen Drähte bestätigen die experimentellen Ergebnisse und unterstützen dabei die Wichtigkeit der Balance zwischen Akzeptor- und Donorgruppen für die Leitfähigkeit der Drähte. Basierend auf diesen Resultaten werden neue Strukturen zur Herstellung vorgeschlagen. Der letzte Teil befasst sich schließlich mit einer unimolekularen Reaktion, die zur Erzeugung einer anomalen Kombination von Pentagon- und Heptagonringen in einem einzelnen organischen Molekül führt. Solche 5-7-Einheiten sind analog zu Stone-Wales-Defekten in Graphen und können elektronische Eigenschaften beachtlich ändern. Die exakte intramolekulare Struktur der Reaktionsprodukte wird durch hochauflösende STM-Bildgebung mit funktionalisierter Spitze eindeutig zugeordnet und zusätzlich durch DFT-Rechnungen bestätigt. / Polycyclic organic molecules and their derivatives present the class of nanostructures that are currently in the focus of scientific research due to their perspectives for the versatile applications in molecular and organic electronics. To exploit their unique properties to full extent, one has to understand the behavior of molecular systems at the nanoscale and to develop a set of fabrication methods. In this work, molecular nanostructures are fabricated using the bottom-up on-surface synthesis approach, which allows precision of the desired products and control over their properties through careful precursors design. To study the reaction flow and the properties of the formed structures, scanning tunneling microscopy (STM) at low temperature and in ultra-high vacuum is the tool of choice. In this work, three molecular systems are studied in detail, with the focus of fabricating atomically precise nanostructures with tailored properties. A cyclodehydrogenation reaction is successfully applied to synthesize an asymmetric starphene molecule in the first part of the work. It is then shown that this molecule can function as a unimolecular NAND logic gate with its response to the attached single Au atoms measured as the position of the electronic resonance. A combination of the atomic and molecular lateral manipulation with the STM tip and scanning tunneling spectroscopy (STS) is used to demonstrate this behavior. The effect of the controllable shifting of the molecular resonances is due to the asymmetric shape of the starphene molecule and was initially predicted theoretically. More complex structures, molecular wires, are presented in the second part of the work by using the surface-assisted Ullmann coupling reaction. The monomer unit, consisting of the alternant donor and acceptor parts, was specifically designed to achieve highly-conductive flexible molecular wires. The conductance is measured by pulling the single wires with the STM tip off the surface. Theoretical calculations of the complex band structure of the wires confirm the obtained results and support the discussion of the importance of the balance between the strength of acceptor and donor units for the conductance of the resultant wires. Based on this, some model structures are proposed. Finally, the last part deals with a unimolecular reaction to create an anomalous combination of pentagon and heptagon rings in a single organic molecule. Such 5-7 moieties are analogous to the Stone-Wales defects in graphene and may significantly alter the electronic properties. The precise intramolecular structure of the reaction products is unambiguously assigned by high-resolution STM imaging with functionalized tips and further confirmed by DFT calculations.

The development of new electronic devices requires the design of novel materials since the existing technologies are not suitable for all applications. In recent years, semiconducting polymers (SCPs) have evolved as fundamental components for the next generation of costumer electronics. They provide interesting features, especially flexibility, light weight, optical transparency and low-cost processability from solution. The research presented in this thesis was devoted to theoretical studies of donor-acceptor (DA) copolymers formed by electron-deficient 3,6-(dithiophene-2-yl)-diketopyrrolo[3,4-c]pyrrole (TDPP) and different electron-rich thiophene compounds. This novel type of SCPs has received a lot of attention due to experimental reports on very good electronic properties which yielded record values for organic field-effect transistor applications. In order to get a deeper understanding of the structural and electronic properties, the main objective of this work was to study this material type on the atomic scale by means of electronic structure methods. For this, density functional theory (DFT) methods were used as they are efficient tools to consider the complex molecular structure. This work comprises three main parts: a comparative study of the structural and the electronic properties of TDPP based DA polymers obtained by means of different theory levels, the calculation of the intermolecular charge transfer between pi-pi stacked DA polymer chains based on the Marcus transfer theory and investigations of molecular p-doping of TDPP based DA polymers. For the first, DFT using different functionals was compared to the density functional based tight binding (DFTB) method, which is computationally very efficient. Although differences in structural properties were observed, the DFTB method was found to be the best choice to study DA polymers in the crystalline phase. For the second, correlations between the molecular structure and the reorganization energy are found. Moreover, the dependency of the electronic coupling element on the spatial shape of the frontier orbitals is shown. Furthermore, a Boltzmann-type statistical approach is introduced in order to enable a qualitative comparison of different isomers and chemical structures. For the last part, the p-doping properties of small, multi-polar dopant molecules with local dipole provided by cyano groups were investigated theoretically and compared with experimental observations. The one with the strongest p-doping properties was studied in this work for the first time on a theoretical basis. Comparing these different p-dopants, rich evidence was found supporting the experimentally observed doping strength.

Organic semiconducting polymers are widely employed in organic electronics such as organic photovoltaics (OPVs), organic field-effect transistors (OFETs) and organic light emitting diodes (OLEDs). Their remarkable mechanical and charge transport properties as well as solution processability allow low-cost fabrication of light-weight and flexible devices. Among them indacenodithiophene (IDT)-based materials are promising candidates for application in organic electronics. Due to their low energetic disorder, extended conjugation and high electron density the IDT-based polymers show high field-effect mobilities and high absorption coefficients. However, their synthesis suffers from long reaction sequences and is often accomplished using toxic materials. Commercialization requires development of more efficient and sustainable reaction pathways to ease tailoring of structures and to limit molecular defects. Herein, the development of new synthetic pathways towards IDT-based polymers is presented in which all C-C coupling steps are achieved by C-H activation – an atom-economic alternative to conventional transition-metal catalyzed cross couplings. Two different strategies were established to synthesize a series of well-defined IDT-based homo- and copolymers with different side chain patterns and varied molecular weights. The first way starts by synthesis of a precursor polymer and subsequent cyclization affording IDT homopolymers. In the second approach, cyclized IDT monomers were prepared first and then polymerized using direct arylation polycondensation (DAP) yielding IDT homo- and copolymers. The synthetic pathways were optimized in terms of maximizing molecular weights and limiting defect structures. While the first pathway enables synthesis of well-defined homopolymers, the latter is the method of choice for preparation of IDT-based copolymers in high yields and adjustable molecular weights. The polymers were further characterized in detail by optical, thermal, electrical and morphological analyses. OFETs as well as all-polymer solar cells (all-PSCs) were fabricated to investigate the influence of structural modifications and molecular weight on their optoelectronic performance. Thus, this thesis provides a comprehensive study of the structure-property correlations of IDT-based polymers and simplified synthetic protocols for the design and preparation of donor-acceptor copolymers in the future.