The π-conjugated organic and polymeric semiconducting materials have attracted much attention in the past years due to their significant potential in applications to electronic and optoelectronic devices including organic field-effect transistors (OFETs), organic photovoltaics (OPVs), and organic light-emitting diodes (OLEDs), etc. Yet, organic and polymeric semiconductors still have challenges associated with their relatively low charge carrier (hole and electron) transport mobilities and ambient stability in OFET applications. This dissertation discusses the molecular engineering on backbones and side-chains of π-conjugated semiconducting polymers to enhance the hole and electron field-effect mobilities. Three donor-acceptor copolymers, the hole transport (p-type) poly(hexathiophene-co-benzo- thiazole) (PBT6), the hole transport poly(thiophenes-benzothiadiazole-thiophenes-diketopyrrolo- pyrrole) (pTBTD), and the electron transport (n-type) poly(dithieno-diketopyrrolopyrrole-bithiazole) (PDBTz) have been developed. Besides, the effect of polymer side chains on polymer solution-processability and charge carrier transport properties was systematically investigated: a side chain 5-decylheptadecyl having the branching position remote from the polymer backbone merges the advantages of the improved solubility from traditional branched side chains in which the branch chains are close to polymer backbone and the effective π-π intermolecular interactions commonly associated with linear side chains. This indicates the potential of side chain engineering to facilitate the charge carrier transport performance of organic and polymeric semiconductors. Additionally, PDBTz solution-processing to OFETs based on non-halogenated solvents (xylenes and tetralin) was studied. The resultant thin-film OFET devices based on non-halogenated solvents exhibited similar film morphology and field-effect electron mobilities as the counterparts based on halogenated solvents, indicative of the feasibility of developing high mobility OFET devices through more environmentally-benign processing.

Conducting polymers that contain metals are remarkable materials, because they have the properties of both organic backbones and metals. Depending on the position of the metal relative to the conjugated backbone, i.e. attached to or directly in the backbone, these two can couple resulting in advancement of the functionality and therefore potential applications of these types of materials. Complexes of tridentate ligands with donor atoms such as phosphorus, nitrogen, and sulfur also have a wide variety of applications. In addition, complexes of tridentate ligands have advantages of stability and control of electron density by variation of donor atoms. Therefore, conjugated polymers with tridentate ligand units will have promise for various applications and advantages in their designs. Complexes of PNP ligand with molybdenum and carbonyl ancillary ligands were synthesized and characterized. Isomerization and conversion reactions between them were investigated as well as the coordination modes. Many types of PNP ligands have been studied in the literature because the hemilabile property of the nitrogen atom promotes some catalytic reactions and gives different coordination geometries. Conducting polymers can be used as redox-active ligands and they can be used to control electron density on the metal attached to them. Synthesis and characterization of a novel polymerizable ligand 3,5-bis-EDOT-N,N-bis[2-diphenylphosphinoethyl]aniline was achieved. Related molybdenum complexes with ancillary ligands as carbonyls were also synthesized and characterized. Monomer complexes and the free ligand were electropolymerized and studied. Tris(bipyridine)ruthenium(II) chloride and analogous complexes have been studied extensively in the literature due to their luminescent and photochemical properties, and excited state lifetimes. Conducting polymers with similar ruthenium groups have been investigated for various applications. Synthesis of four ruthenium complexes with the polymerizable ligand 2,6-Bis[4-[2-(3,4-diethylenedioxy)thiophene]pyrazol-1-yl]pyridine and four different bidentate ligands were reproduced; electropolymerizations of the complexes were achieved; electrochemical, UV-Vis and luminescence studies were performed and discussed. Various complexes of copper, silver, platinum, and palladium with nitrogen and phosphorus donors have been reported for their luminescence behavior as well as their interesting structures. Model complexes of these metals with N,N-bis[2-(diphenylphosphino)ethyl]phenyl-amine (a PNP ligand) have been synthesized and characterized. Absorption and luminescence behaviors as well as the coordination modes were investigated. / text

We present an improved model of charge carrier photogeneration in π-conju- gated polymers with weak intermolecular interactions based on the model of Arkhipov. It includes quantum effects affecting the creation of charge transfer states, which occurs as an intermediate step in the free charge carrier photo- generation process. The electrostatic potential between the electron and the hole and transfer integrals needed for the calculation of the potential barrier for the charge transfer state dissociation are calculated quantum-chemically. We apply our model on experimental data of the charge carrier photogenera- tion efficiency in poly[1-trimethylsilylphenyl,2-phenyl]acetylene to explain its dependence on applied electric field. We eliminate several problems of the previous model. We are able to fit experimental data with just one set of parameters in the whole interval of the applied electric field. We do not have to consider several intervals of the electric field separately as in the previous work and reduce the number of needed parameters to three. Key words π-conjugated polymers, charge carrier photogeneration, photoconductivity 1

For several decades, the field of magneto-optics (MO) has demonstrated applications that have impact on every day applications such as in optical data storage, magnetic field sensing, crucial for magnetoencephalography and magnetocardiography; and compact and efficient optical isolators, among others. In the past, many of these applications and the devices designed for them have heavily relied on inorganic materials. Organic materials with a high MO response represent an interesting alternative to the inorganic equivalent by not only being a more cost efficient solution, but also by allowing the user to modify a number of variables to control and optimize the MO performance depending on the application and level of performance desired. In this dissertation I discuss the MO properties of novel organic materials, starting with polythiophene, which has been of interest due to the strong relationship between its high MO performance and its lamellar structure and regioregularity. I will also be discussing another material system that provides several degrees of MO tunability: magnetite based nanocomposites. A unique and novel synthetic approach described in this dissertation yields both highly transparent and MO responsive polymer films. I will be describing a systematic approach that indicates a strong influence of the size of the nanoparticle as well as the nanoparticle concentration in the MO performance of the bulk polymer, while maintaining high optical quality with minimal scattering and absorption in the visible and near infrared. Finally, I will be discussing the implementation of both a magnetite nanocomposite and a cobalt ferrite based nanocomposite in a free space magnetic field system and demonstrate the proof-of-principle operation of a sensing system.

A theoretical model describing photophysics of π-conjugated aggregates, such as molecular crystals and polymer thin films, is developed. A Holstein-like Hamiltonian expressed with a multi-particle basis set is used to evaluate absorption and photoluminescence (PL) spectra. An analysis with line strength ratio proves to be a powerful diagnostic tool to obtain additional spectral signatures with which to distinguish H- vs. J-aggregation. For the H-aggregates absorption peak ratio, A0-0/A0-1, diminishes as the excitonic coupling increases. Also the PL peak ratio, I0-0/I0-1, is zero at T=0K with no disorder and the value increases as temperature and disorder increase. By contrast the J-aggregates show the opposite trends. Furthermore we will show the PL peak ratio provides a direct measurement of the exciton coherence length for a linear J-aggregate and could be expressed as I0-0/I0-1 = Ncoh/l2. We will also show that it is inversely proportional to square root of temperature (T-1/2). Applying our theory to the herringbone style oligoacene molecular crystals, we show the lowest singlet exciton states are highly influenced by charge transfer (CT) states and the well known energetic gap in two polarized absorption spectra, so called Davydov Splitting (DS), is a product of the interaction. We have successfully reproduced the DS for all three oligoacenes without any free parameters. Inspired by the CT contribution in oligoacene crystals, we further develop Wannier-Mott exciton model and apply to disorder-free polydiacetylene (PDA) quantum wires, which have been shown to be extremely emissive. We will show the quantum wire is a J-aggregate and we once again derive the peak ratio and the coherence size relation, I0-0/I0-1 = kNcoh/l2, where k is a prefactor close to unity. Typical photophysical properties of polymer p-stacks such as those occurring in P3HT films are well explained by the simple linear H-aggregate model. However several groups have started seeing more J-like behaviors amongst “improved” (less disordered) polymer films such as increased values of A0-0/A0-1 and I0-0/I0-1 and higher radiative rates. With the new perception of a single polymer chain being a J-aggregate, we apply our new theory to p-stack of polymer chains. We call this HJ-aggregate model since the interchain interaction induces H-aggregation. In the study we show a competition between intrachain and interchain interactions that leads to unique photophysical features. The new model is capable of explaining a wide range of polymer systems and most importantly the theory uncovers the mechanism of the improved polymer films; reducing disorder urges increasing intrachain reactions within each chain, thus enhancing more J-like spectral features. / Chemistry

L'élaboration de réseaux poreux pi-conjugués par l'auto-organisation de molécules organiques, les cyclotriphosphazènes spirocycliques, a été explorée. L'étude de la stabilité des réseaux obtenus à partir du tris(o-phénylènedioxy)cyclotriphosphazène (TPP) conjointement à l'étude de la réactivité du N3P3Cl6 face à l'attaque nucléophile de différents dérivés du catéchol ont permis de définir de nouvelles cibles. Dans ce cadre, un nouveau composé, le tris(2,3-triphénylènedioxy)cyclotriphosphazène (TTPP) dans lequel le motif central est substitué par trois systèmes pi-conjugués étendus de type triphénylène a été synthétisé. Les tectons TTPP, de symétrie C3, présentent une orientation atypique des motifs aromatiques. Leur forme, analogue à celle d'une roue à aubes, leur permet d'engendrer à l'état cristallin des lacunes sous forme de deux types de nano-canaux de respectivement 6,1 Å et 8,4 Å de large et 10,7 Å et 12,4 Å de large, pouvant inclure des molécules de 1,2,4-trichlorobenzène. Ce matériau contient la plus grande porosité obtenu à partir de cyclotriphosphazènes spirocycliques à ce jour. La formation de réseaux poreux chiraux a également été réalisée à partir de tectons portant chacun trois motifs (S)-binol. Le (S,S,S)-tribinolcyclotriphosphazène ((S,S,S)-TBP) a ainsi pu être co-cristallisé avec des molécules d'o-xylène. Ainsi, des informations permettant de mieux comprendre la structure moléculaire de cyclotriphosphazènes portant des spirocycles à sept chaînons ont été obtenues. Enfin, les propriétés optoélectroniques des tectons ont été étudiées en solution. L'influence de l'agent directeur cyclotriphosphazène sur les propriétés optiques des chromophores a, en particulier, été abordée. / Elaboration of pi-conjugated networks through self-organization of spirocyclic cyclotriphosphazene molecules has been explored. The stability of the networks built from described tris(o-phenylenedioxy)cyclotriphosphazene (TPP) jointly with the study of the reactivity of N3P3Cl6 undergoing nucleophilic attack by catechol derivatives allowed to design new tectons. In this context, a new tris(2,3-triphenylenedioxy)cyclotriphosphazene (TTPP) compound embedding a central hub substituted by pi-conjugated triphenylene unit has been synthesized. TTPP tectons exhibits a particular shape with specific orientation of aromatic units. Their paddle-wheel like shape allows the elaboration of a porous network having two types of nano-tunnels of respectively 6.1 Å and 8.4 Å large and 10.7 Å and 12.4 Å large. This material has the biggest channel size described for network build from spirocyclic cyclotriphosphazenes and inclusion compounds with 1,2,4-trich lorobenzene molecules were made. Elaboration of chiral porous network from tectons constituted by three (S)-binol units has also been realized. Tribinolcyclotriphosphazene has been co-cristallized with o-xylene molecules. Thus, useful informations on seven-membered spirocyclic cyclotriphosphazene molecular structure have been obtained. Finally, tectons opto-electronic properties have been studied in solution. Influence of the cyclotriphosphazene directing agent on optical chromophore properties has been a particular matter of attention.

Le couplage covalent de précurseurs moléculaires spécialement conçus, assisté par une surface métallique, a récemment émergé comme nouvelle voie pour la création de nouvelles architectures moléculaires prometteuses pour l’électronique moléculaire. Les phtalocyanines et leurs dérivés ont attiré beaucoup d’intérêt à cause de leurs propriétés chimiques et optoélectroniques. Dans cette thèse la synthèse de composés de phtalocyanine est présentée. Les composés sont obtenus par une réaction en surface entre précurseurs fonctionnalisés avec quatre groupements carbonitriles et des atomes métalliques. L’étude expérimentale est faite par microscopie à effet tunnel et spectroscopie de photoémission X. Les précurseurs moléculaires de TCN-DBTTF et de PPCN ont été étudiés. Les TCN-DBTTF ont été déposés avec les atomes de Mn, Fe ou Cu sur Ag(111) et Au(111). La réaction de cyclotetramerization a été activée par recuits. Dans le cas le plus favorable (TCN-DBTTF avec Fe sur Ag(111)), la réaction peut être activée à 200°C et permet la synthèse de phtalocyanines individuelles. Un recuit à plus haute température permet de continuer la réaction en 1D (250°C) et en 2D (275°C). Des résultats similaires ont été obtenus pour le dépôt de PPCN avec Mn ou Cu sur Au(111). L’évolution des spectres des niveaux de coeur permet d’obtenir une preuve de la réaction. Les différents facteurs qui influencent la cyclotetramerisation ont été étudiés.L'étude démontre la versatilité de la méthode: la synthèse en surface permet la création de polymères 2D originaux connectés par des macrocycles de phtalocyanine susceptibles d’être étendus à un grand nombre de précurseurs et d’atomes métalliques. / Surface-assisted covalent coupling of suitably designed molecular precursors on metal surfaces has recently emerged as a new route towards the design of novel molecular architectures promising for future applications. Phthalocyanines and their derivatives have been widely studied for their chemical and optoelectronic properties. In this thesis the synthesis of phthalocyanine compounds is presented. The compounds are obtained through an on-surface reaction between tetracarbonitrile-functionalized precursors and metals. The experimental investigation is carried out by means of scanning tunnelling microscopy and X-Ray photoemission spectroscopy. Two molecular precursors, TCN-DBTTF and PPCN, are studied. TCN-DBTTF molecules are deposited with metal atoms (Mn, Fe, or Cu) on Ag(111) and Au(111). Annealing is used to activate the reaction of cyclotetramerization between precursors and metals. In the most favourable case (TCN-DBTTF with Fe on Ag(111)) the reaction can be activated at 200°C and leads to the synthesis of individual phthalocyanines. Increasing the temperature allows the synthesis of polymeric lines, at 250°C, and small 2D domains, at 275°C. Similar results are obtained for PPCN deposition with Mn or Cu on Au(111). In this latter case, the evolution of core level spectra allows a chemical proof of the on-surface reaction. The factors affecting on-surface cyclotetramerization have also been studied. This study demonstrates the versatility of the method: on-surface cyclotetramerization allows creating original 2D polymers connected by phthalocyanine macrocycles, and may work with a wide range of tetracarbonitrile-functionalized precursors and metallic atoms.

De nouveaux matériaux π-conjugués fonctionnels ont été élaborés selon deux approches. La première a consisté à préparer des molécules π-conjuguées fonctionnelles – basées sur un segment central de type 1,4-bis(phénylène-éthynyl)benzène – permettant de développer des nano-objets et des nanomatériaux hybrides associant les segments conjugués organiques à d'autres composantes : des nanotubes de carbone et de la silice sous la forme de nanoparticules ou de nanomatériaux. Le segment conjugué de base a été fonctionnalisé soit directement, soit par le biais de ses chaînes solubilisantes. La seconde approche a permis de développer une nouvelle famille d'oligomères conjugués organiques et solubles – basés sur des motifs de type thiénopyrazine – de faible gap énergétique entre les orbitales HOMO et LUMO. Les propriétés électro-optiques de ces composés exclusivement organiques ont été confrontées à des calculs prédictifs obtenus par des méthodes de la chimie théorique (DFT, TDFFT). Ces matériaux hybrides fonctionnels ont pu être valorisés. La fonctionnalisation des chaînes solubilisantes par des groupements ioniques imidazolium ont permis la conception de nouveaux matériaux polyélectrolytes pour accéder à des ionogels. La fonctionnalisation du segment conjugué en lui-même a pu être mis à profit pour la fonctionnalisation covalente de nanotubes de carbone ou de nanoparticules de silice. / New π-conjugated functional materials were elaborated in two ways. The first one consisted in the preparation of π-conjugated functional molecules – based on a 1,4-bis(phenylene-ethynyl)benzene central segment – in order to develop hybrid nano-objects and nanomaterials which combine organic conjugated segments with other components : carbon nanotubes or silica (nanoparticules, nanomaterials). The central conjugated unit is functionalized either on this π-conjugated system or at the end of the side chains. The second approach allows the development of a new family of organic soluble conjugated oligomers – based on thienopyrazine units – characterized by a low band gap between HOMO and LUMO orbitals. The electronic and optic properties of these organic compounds were compared to theoretical calculations (DFT, TDFFT). The functionalization of the side chains by ionic imidazolium units could permit the conception of new polyelectrolyte materials and open the access to new ionogel materials. The functionalization of the conjugated segment was used with advantage for the covalent functionalization of carbon nanotubes or silica nanoparticules.

No description available.

In this thesis we explore in particular the dynamics of a special type of quasi-particle in pi-conjugated materials termed polaron, the origin of which is intimately related to the strong interactions between the electronic and the vibrational degrees of freedom within these systems. In order to conduct such studies with the particular focus of each appended paper, we simultaneously solve the time-dependent Schrödinger equation and the lattice equation of motion with a three-dimensional extension of the famous Su-Schrieffer-Heeger (SSH) model Hamiltonian. In particular, we demonstrate in Paper I the applicability of the method to model transport dynamics in molecular crystals in a region were neither band theory nor perturbative treatments such as the Holstein model and extended Marcus theory apply. In Paper II we expand the model Hamiltonian to treat the revolution of phenylene rings around the sigma-bonds and demonstrate the great impact of stochastic ring torsion on the intra-chain mobility in conjugated polymers using poly[phenylene vinylene] (PPV) as a model system. Finally, in Paper III we go beyond the original purpose of the methodology and utilize its great flexibility to study radiationless relaxations of hot excitons. / Report code: LiU-TEK-LIC-2007:4.