Liquid crystalline hexabenzocoronenes as organic molecular materials - synthesis, characterization and application

Die vorliegende Arbeit 'Liquid Crystalline Hexabenzocoronenes as Organic Molecular Materials - Synthesis, Characterization and Application' war durch drei Schwerpunkte definiert:1. Verbesserung der Synthese von Hexabenzocoronen Derivaten mit sechsfacher Alkyl-Substitution,2. Entwicklung von molekularen Materialien mit verbesserten Eigenschaften wie zum Beispiel Löslichkeit und Verarbeitbarkeit,3. Einsatz der entwickelten Moleküle in optoelektronischen Bauteilen wie zum Beispiel organischen Solarzellen und Feld-Effekt-Transistoren.Mit Hilfe einer neuen Syntheseroute ist es gelungen Aryl-Aryl und Aryl-Alkyl Kupplungen sehr spät in der Reaktionssequenz von Hexabenzocoronenen einzusetzen. Dies führte zu einer Vielzahl substituierter HBC Derivate. Die Einführung eines Phenyl Spacers zwischen den HBC Kern und die äußeren Alkylketten, wie zum Beispiel in HBC-PhC12, hatte eine Vielzahl positiver Effekte wie dramatisch verbesserte Löslichkeit und Flüssigkristallinität bei Raumtemperatur zur Folge. Die Kombination dieser Phänomene ermöglichte die Bildung hochgeordneter Filme, welche sehr wichtig für den Einsatz in organischen Bauelementen sind. Mit Hilfe von STM Techniken an der Fest-Flüssig Phasengrenze wurden hochgeordnete 2-D Strukturen der HBC Moleküle gefunden. Die Kombination von extrem hoher kolumnarer Ordnung, bestimmt mit Hilfe der Festkörper NMR Spektroskopie, mit einer konstant hohen Ladungsträgerbeweglichkeit, führte zu dem sehr erfolgreichen Einsatz von HBC-PhC12 in organischen Solarzellen.

Self assembled monolayers for engineering of structured inorganic materials in the micrometer and submicrometer range

Deutsch:In der vorliegenden Arbeit konnten neue Methoden zur Synthese anorganischer Materialien mit neuartiger Architektur im Mikrometer und Nanometer Maßstab beschrieben werden. Die zentrale Rolle der Formgebung basiert dabei auf der templatinduzierten Abscheidung der anorganischen Materialien auf selbstorganisierten Monoschichten. Als Substrate eignen sich goldbedampfte Glasträger und Goldkolloide, die eine Mittelstellung in der Welt der Atome bzw. Moleküle und der makroskopischen Welt der ausgedehnten Festkörper einnehmen. Auf diesen Substraten lassen sich Thiole zu einer monomolekularen Schicht adsorbieren und damit die Oberflächeneigenschaften des Substrates ändern. Ein besonderer Schwerpunkt bei dieser Arbeit stellt die Synthese speziell auf die Bedürfnisse der jeweiligen Anwendung ausgerichteten Thiole dar.Im ersten Teil der Arbeit wurden goldbedampfte Glasoberflächen als Template verwendet. Die Abscheidung von Calciumcarbonat wurde in Abhängigkeit der Schichtdicke der adsorbierten Monolage untersucht. Aragonit, eine der drei Hauptphasen des Calciumcarbonat Systems, wurde auf polyaromatischen Amid - Oberflächen mit Schichtdicken von 5 - 400 nm Dicke unter milden Bedingung abgeschieden. Die einstellbaren Parameter waren dabei die Kettenlänge des Polymers, der w-Substituent, die Bindung an die Goldoberfläche über Verwendung verschiedener Aminothiole und die Kristallisationstemperatur. Die Schichtdickeneinstellung der Polymerfilme erfolgte hierbei über einen automatisierten Synthesezyklus.Titanoxid Filme konnten auf Oberflächen strukturiert werden. Dabei kam ein speziell synthetisiertes Thiol zum Einsatz, das die Funktionalität einer Styroleinheit an der Oberflächen Grenze als auch eine Möglichkeit zur späteren Entfernung von der Oberfläche in sich vereinte. Die PDMS Stempeltechnik erzeugte dabei Mikrostrukturen auf der Goldoberfläche im Bereich von 5 bis 10 µm, die ihrerseits über die Polymerisation und Abscheidung des Polymers in den Titanoxid Film überführt werden konnten. Drei dimensionale Strukturen wurden über Goldkolloid Template erhalten. Tetraethylenglykol konnte mit einer Thiolgruppe im Austausch zu einer Hydroxylgruppe monofunktionalisiert werden. Das erhaltene Molekül wurde auf kolloidalem Gold selbstorganisiert; es entstand dabei ein wasserlösliches Goldkolloid. Die Darstellung erfolgte dabei in einer Einphasenreaktion. Die so erhaltenen Goldkolloide wurden als Krstallisationstemplate für die drei dimensionale Abscheidung von Calciumcarbonat verwendet. Es zeigte sich, dass Glykol die Kristallisation bzw. den Habitus des krsitalls bei niedrigem pH Wert modifiziert. Bei erhöhtem pH Wert (pH = 12) jedoch agieren die Glykol belegten Goldkolloide als Template und führen zu sphärisch Aggregaten. Werden Goldkolloide langkettigen Dithiolen ausgesetzt, so führt dies zu einer Aggregation und Ausfällung der Kolloide aufgrund der Vernetzung mehrer Goldkolloide mit den Thiolgruppen der Alkyldithiole. Zur Vermeidung konnte in dieser Arbeit ein halbseitig geschütztes Dithiol synthetisiert werden, mit dessen Hilfe die Aggregation unterbunden werden konnte. Das nachfolgende Entschützten der Thiolfunktion führte zu Goldkolloiden, deren Oberfläche Thiol funktionalisiert werden konnte. Die thiolaktiven Goldkolloide fungierten als template für die Abscheidung von Bleisulfid aus organisch/wässriger Lösung. Die Funktionsweise der Schutzgruppe und die Entschützung konnte mittels Plasmonenresonanz Spektroskopie verdeutlicht werden. Titanoxid / Gold / Polystyrol Komposite in Röhrenform konnten synthetisiert werden. Dazu wurde ein menschliches Haar als biologisches Templat für die Formgebung gewählt.. Durch Bedampfung des Haares mit Gold, Assemblierung eines Stryrolmonomers, welches zusätzlich eine Thiolfunktionalität trug, Polymerisation auf der Oberfläche, Abscheidung des Titanoxid Films und anschließendem Auflösen des biologischen Templates konnte eine Röhrenstruktur im Mikrometer Bereich dargestellt werden. Goldkolloide fungierten in dieser Arbeit nicht nur als Kristallisationstemplate und Formgeber, auch sie selbst wurden dahingehend modifiziert, dass sie drahtförmige Agglormerate im Nanometerbereich ausbilden. Dazu wurden Template aus Siliziumdioxid benutzt. Zum einen konnten Nanoröhren aus amorphen SiO2 in einer Sol Gel Methode dargestellt werden, zum anderen bediente sich diese Arbeit biologischer Siliziumoxid Hohlnadeln aus marinen Schwämmen isoliert. Goldkolloide wurden in die Hohlstrukturen eingebettet und die Struktur durch Ausbildung von Kolloid - Thiol Netzwerken mittels Dithiol Zugabe gefestigt. Die Gold-Nanodrähte im Bereich von 100 bis 500 nm wurden durch Auflösen des SiO2 - Templates freigelegt.

Supramolecular order and dynamics of discotic materials studied by solid-state NMR recoupling methods

The topic of this thesis is the investigation of structure,order and dynamics in discotic mesogens by advancedsolid-state NMR spectroscopy. Most of the discotic mesogensunder investigation are hexa-peri-hexabenzocoronene (HBC)derivatives which are of particular interest for potentialdevice applications due to their high one-dimensional chargecarrier mobilities. The supramolecular stacking arrangement of the discoticcores was investigated by 2D 1H-1H double-quantum (DQ)methods, which were modified by incorporating the WATERGATEsuppression technique into the experiments in order toovercome severe phase problems arising from the strongsignal of the long alkyl sidechains. Molecular dynamics and sample orientation was probed throughthe generation of sideband patterns by reconversion rotorencoding in 2D recoupling experiments. These experimentswere extended by new recoupling schemes to enable thedistinction of motion and orientation effects. The solid-state NMR studies presented in this work aim tothe understanding of structure-property relationships in theinvestigated discotic materials, while the experimentsapplied to these materials include new recoupling schemeswhich make the desired information on molecular orientationand dynamics accessible without isotope labelling.

New discotic liquid crystals based on large polycyclic aromatic hydrocarbons as materials for molecular electronics

A series of new columnar discotic liquid crystalline materials based on the superphenalene (C96) core has been synthesized by oxidative cyclodehydrogenation with iron(III) chloride of suitable three-dimensional oligophenylene precursors. These compounds were investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide angle X-ray scattering (WAXS), and showed highly ordered supramolecular arrays and mesophase behavior over a broad temperature range. Good solubility, through the introduction of long alkyl chains, and the fact that these new superphenalene derivatives were found to be liquid crystalline at room temperature enabled the formation of highly ordered films (using the zone-casting technique), a requirement for application in organic electronic devices. The one-dimensional, intracolumnar charge carrier mobilities of superphenalene derivatives were determined using the pulse-radiolysis time-resolved microwave conductivity technique (PR-TRMC). Electrical properties of different C96-C12 architectures on mica surfaces were examined by using Electrostatic Force Microscopy (EFM) and Kelvin Probe Force Microscopy (KPFM). Hexa-peri-hexabenzocoronene (C42) derivatives substituted at the periphery with six branched alkyl ether chains were also synthesized. It was found that the introduction of ether groups within the side chains enhances the affinity of the discotic molecules towards polar surfaces, resulting in homeotropic self-assembly (as shown by POM and 2D-WAXS) when the compounds are processed from the isotropic state between two surfaces. A new, insoluble, superphenalene building block bearing six reactive sites was prepared, and was further used for the preparation of dendronized superphenalenes with bulky dendritic substituents around the core. UV/Vis and fluorescence experiments suggest reduced π-π stacking of the superphenalene cores as a result of steric hindrance between the peripheral dendritic units. A new family of graphitic molecules with partial ”zig-zag” periphery has been established. The incorporation of ”zig-zag” edges was shown to have a strong influence on the electronic properties of the new molecules (as studied by solution and solid-state UV/Vis, and fluorescence spectroscopy), leading to a significant bathochromic shift with respect to the parent PAHs (C42 and C96). The reactivity of the additional double bonds was examined. The attachment of long alkyl chains to a ”zig-zag” superphenalene core afforded a new, processable, liquid crystalline material.

1-, 2- and 3-dimensional phenylene-based materials for optoelectronic applications

A series of oligo-phenylene dendronised conjugated polymers was prepared. The divergent synthetic approach adopted allowed for the facile synthesis of a range of dendronised monomers from a common intermediate, e.g. first and second generation fluorene. Only the polymerisation of the first generation and alkylarylamine substituted dendronised fluorene monomers yielded high molecular weight materials, attributed to the low solubility of the remaining dendronised monomers. The alkylarylamine substituted dendronised poly(fluorene) was incorporated into an organic light emitting diode (OLED) and exhibited an increased colour stability in air compared to other poly(fluorenes). The concept of dendronisation was extended to poly(fluorenone), a previously insoluble material. The synthesis of the first soluble poly(fluorenone) was achieved by the incorporation of oligo-phenylene dendrons at the 4-position of fluorenone. The dendronisation of fluorenone allowed for a polymer with an Mn of 4.1 x 104 gmol-1 to be prepared. Cyclic voltammetry of the dendronised poly(fluorenone) showed that the electron affinity of the polymer was high and that the polymer is a promising n-type material. A dimer and trimer of indenofluorene (IF) were prepared from the monobromo IF. These oligomers were investigated by 2-dimensional wide angle x-ray spectroscopy (2D-WAXS), polarised optical microscopy (POM) and dielectric spectroscopy, and found to form highly ordered smetic phases. By attaching perylene dye as the end-capper on the IF oligomers, molecules that exhibited efficient Förster energy transfer were obtained. Indenofluorene monoketone, a potential defect structure for IF based OLED’s, was synthesised. The synthesis of this model defect structure allowed for the long wavelength emission in OLED’s to be identified as ketone defects. The long wavelength emission from the indenofluorene monoketone was found to be concentration dependent, and suggests that aggregate formation is occurring. An IF linked hexa-peri-hexabenzocoronene (HBC) dimer was synthesised. The 2D-WAXS images of this HBC dimer demonstrate that the molecule exhibits intercolumnar organisation perpendicular to the extrusion direction. POM images of mixtures of the HBC dimer mixed with an HBC with a low isotropic temperature demonstrated that the HBC dimer is mixing with the isotropic HBC.

Discotic materials for organic electronics

Die Kontrolle der ausgeprägten Aggregationsfähigkeit von alkylsubstituierten Hexa-peri-hexabenzocoronenen (HBC) wurde durch die Reduktion der intermolekularen Wechselwirkungen erreicht. Sterisch anspruchsvolle, verzweigte Alkylketten, mit einem Verzweigungspunkt naher des aromatischen Kerns, wurden in die Corona der aromatischen Scheiben eingebracht und verleihen den Derivaten Schmelzbarkeit ohne thermische Zersetzung. Dies erlaubte eine kostengünstige Verarbeitungstechniken direkt aus der Schmelze wie z.B. Zonenschmelzen, um uniaxial organisierte makroskopische Filme zu erhalten. Abhängig von dem sterischen Anspruch, der durch die Seitenkette erzeugt wird, wurden unterschiedliche molekulare Orientierungen auf Oberflächen erhalten, was eine wichtige Voraussetzung ist, um diskotische Materialien in elektronische Bauteile zu implementieren. Eine weitere Voraussetzung sind hohe Ladungsträgerbeweglichkeiten und Ladungsträgerlebenszeiten in den Halbleitermaterialien, die mit time-resolved pulse-radiolysis microwave conductivity (TR-PRMC) und time-of-flight (TOF) auch für die synthetisieren Materialien bestimmt wurden. Die neuen Materialien zeigten bereits in organischen Solarzellen gute Leistungen. Den Einfluss des Perimeters auf die elektronischen Eigenschaften der polyzyklischen aromatischen Kohlenwasserstoffe (PAKs) wurde theoretisch vorhergesagt und in dieser Arbeit durch die Synthese einer homologe Serie von PAKs experimentell bestätigt. Geht man von der „arm-chair“ Peripherie des HBC sukzessive zu einer partiellen „zickzack“ Peripherie, so findet man eine Abhängigkeit der elektronischen Banden von Symmetrie und Größe des aromatischen Systems. Die spontan ausgebildete Überstruktur dieser Derivate zeigte eine Abhängigkeit von Substitutionsmuster und der Natur der Alkylketten. Zusammenfassend wurden neben der Synthese von neuartigen Materialien für den Einsatz in der organischen Elektronik Synthesen entwickelt, die eine vereinfachte Funktionalisierung von ausgedehnten PAKs ermöglicht. Diese Konzepte erlauben eine Justierung der molekularen und supramolekularen Eigenschaften, eines der wichtigsten Voraussetzungen für den Einsatz von Materialien in elektronischen Bauelementen.

Structure and properties of composite polyolefin materials

This thesis is based on three main studies, all dealing with structure-property investigation of semicrystalline polyolefin-based composites. Low density poly(ethylene) (LDPE) and isotactic poly(propylene) (iPP) were chosen as parts of the composites materials and they were investigated either separately (as homoploymers), either in blend systems with the composition LDPE/iPP 80/20 or as filled matrix with layered silicate (montmorillonite). The beneficial influence of adding ethylene-co-propylene polymer of amorphous nature, to low density poly(ethylene)/isotactic poly(propylene) (80/20) blend is demonstrated. This effect is expressed by the major improvement of mechanical properties of ternary blends as examined at a macroscopic size scale by means of tensile measurements. The structure investigation also reveals a clear dependence of the morphology on adding ethylene-copropylene polymer. Both the nature and the content of ethylene-co-propylene polymer affect structure and properties. It is further demonstrated that the extent of improvement in mechanical properties is to be related to the molecular details of the compatibilizer. Combination of high molecular weight and high ethylene content is appropriate for the studied system where the poly(ethylene) plays the role of matrix. A new way to characterize semicrystalline systems by means of Brillouin spectroscopy is presented in this study. By this method based on inelastic light scattering, we were able to measure the high frequency elastic constant (c11) of the two microphases in the case where the spherulites size is exhibit size larger than the size of the probing phonon wavelength. In this considered case, the sample film is inhomogeneous over the relevant length scales and there is an access to the transverse phonon in the crystalline phase yielding the elastic constant c44 as well. Isotactic poly(propylene) is well suited for this type of investigation since its morphology can be tailored through different thermal treatment from the melt. Two distinctly different types of films were used; quenched (low crystallinity) and annealed (high crystallinity). The Brillouin scattering data are discussed with respect to the spherulites size, lamellae thickness, long period, crystallinity degree and well documented by AFM images. The structure and the properties of isotactic poly(propylene) matrix modified by inorganic layered silicate, montmorillonite, are discussed with respect to the clay content. Isotactic poly(propylene)-graft-maleic anhydride was used as compatibilizer. It is clearly demonstrated that the property enhancement is largely due to the ability of layered silicate to exfoliate. The intimate dispersion of the nanometer-thick silicate result from a delicate balance of the content ratio between the isotactic poly(propylene)-graft-maleic anhydride compatibilizer and the inorganic clay.

Conjugated semiconducting organic materials for electronic applications

Since conjugated polymers, i.e. polymers with spatially extended pi-bonding system have offered unique physical properties, unobtainable for conventional polymers, significant research efforts directed to better understanding of their chemistry, physics and engineering have been undertaken in the past two and half decades. In this thesis we discuss the synthesis, characterisation and investigation of conjugated semiconducting organic materials for electronic applications. Owing to the versatile properties of metal-organic hybrid materials, there is significant promise that these materials can find use in optical or electronic devices in the future. In addressing this issue, the synthesis of bisthiazol-2-yl-amine (BTA) based polymers is attempted and their metallation is investigated. The focus of this work has been to examine whether the introduction of coordinating metal ions onto the polymer backbone can enhance the conductivity of the material. These studies can provide a basis for understanding the photophysical properties of metal-organic polymers based on BTA. In their neutral (undoped) form conjugated polymers are semiconductors and can be used as active components of plastics electronics such as polymer light-emitting diodes, polymer lasers, photovoltaic cells, field-effect transistors, etc. Toward this goal, it is an objective of the study to synthesize and characterize new classes of luminescent polymeric materials based on anthracene and phenanthrene moieties. A series of materials based on polyphenylenes and poly(phenyleneethynylene)s with 9,10-anthrylene subunits are not only presented but the synthesis and characterization of step-ladder and ladder poly(p-phenylene-alt-anthrylene)s containing 9,10-anthrylene building groups within the main chain are also explored. In a separate work, a series of soluble poly-2,7- and 3,6-phenanthrylenes are synthesized. This can enable us to do a systematic investigation into the optical and electronic properties of PPP-like versus PPV-like. Besides, the self-organization of 3,6-linked macrocyclic triphenanthrylene has been investigated by 2D wide-angle X-ray scattering experiments performed on extruded filaments in solution and in the bulk. Additionally, from the concept that donor-acceptor materials can induce efficient electron transfer, the covalent incorporation of perylene tetracarboxydiimide (PDI) into one block of a poly(2,7-carbazole) (PCz)-based diblock copolymer and 2,5-pyrrole based on push-pull type material are achieved respectively.

Nitrogen-bridged polyphenylene-based materials for electronic applications

Conjugated polymers are macromolecules that possess alternating single and double bonds along the main chain. These polymers combine the optoelectronic properties of semiconductors with the mechanical properties and processing advantages of plastics. In this thesis we discuss the synthesis, characterization and application of polyphenylene-based materials in various electronic devices. Poly(2,7-carbazole)s have the potential to be useful as blue emitters, but also as donor materials in solar cells due to their better hole-accepting properties. However, it is associated with two major drawbacks (1) the emission maximum occurs at 421 nm where the human eye is not very sensitive and (2) the 3- and 6- positions of carbazole are susceptible to chemical or electrochemical degradation. To overcome these problems, the ladder-type nitrogen-bridged polymers are synthesized. The resulting series of polymers, nitrogen-bridged poly(ladder-type tetraphenylene), nitrogen-bridged poly(ladder-type pentaphenylene), nitrogen-bridged poly(ladder-type hexaphenylene) and its derivatives are discussed in the light of photophysical and electrochemical properties and tested in PLEDs, solar cell, and OFETs. A promising trend which has emerged in recent years is the use of well defined oligomers as model compounds for their corresponding polymers. However, the uses of these molecules are many times limited by their solubility and one has to use vapor deposition techniques which require high vacuum and temperature and cannot be used for large area applications. One solution to this problem is the synthesis of small molecules having enough alkyl chain on the backbone so that they can be solution or melt processed and has the ability to form thin films like polymers as well as retain the high ordered structure characteristics of small molecules. Therefore, in the present work soluble ladderized oligomers based on thiophene and carbazole with different end group were made and tested in OFET devices. Carbazole is an attractive raw material for the synthesis of dyes since it is cheap and readily available. Carbazoledioxazine, commercially known as violet 23 is a representative compound of dioxazine pigments. As part of our efforts into developing cheap alternatives to violet 23, the synthesis and characterization of a new series of dyes by Buchwald-type coupling of 3-aminocarbazole with various isomers of chloroanthraquinone are presented.

Supramolecular order and dynamics of functional materials studied by solid state NMR

The goal of this thesis was the investigation of the structure, conformation, supramolecular order and molecular dynamics of different classes of functional materials (phthalocyanine, perylene and hexa-peri-hexabenzocoronene derivatives and mixtures of those), all having planar aromatic cores modified with various types of alkyl chains. The planar aromatic systems are known to stack in the solid and the liquid-crystalline state due to p-p interactions forming columnar superstructures with high one-dimensional charge carrier mobility and potential application in photovoltaic devices. The different functionalities attached to the aromatic cores significantly influence the behavior of these systems allowing the experimentalists to modify the structures to fine-tune the desired thermotropic properties or charge carrier mobility. The aim of the presented studies was to understand the interplay between the driving forces causing self-assembly by relating the structural and dynamic information about the investigated systems. The supramolecular organization is investigated by applying 1H solid state NMR recoupling techniques. The results are related with DSC and X-ray scattering data. Detailed information about the site-specific molecular dynamics is gained by recording spinning sideband patterns using 1H-1H and 13C-1H solid state NMR recoupling techniques. The determined dipole-dipole coupling constants are then related with the coupling constants of the respective rigid pairs, thus providing local dynamic order parameters for the respective moieties. The investigations presented reveal that in the crystalline state the preferred arrangement in the columnar stack of discotic molecules modified with alkyl chains is tilted. This leads to characteristic differences in the 1H chemical shifts of otherwise chemically equivalent protons. Introducing branches and increasing the length of the alkyl chains results in lower mesophase transitions and disordered columnar stacks. In the liquid-crystalline state some of the discs lose the tilted orientation, others do not, but all start a rapid rotation about the columnar axis.

Synthesis of hexa-peri-hexabenzocoronenes - from building blocks to functional materials

Discotic hexa-peri-hexabenzocoronene (HBC) derivatives have attracted intensive scientific interest due to their unique optoelectronic properties, which depends, to a large extend, upon the attached functional groups. The presented work covers the synthesis of novel HBC building blocks and new HBC derivatives as functional materials. The traditional preparation of HBC derivatives requires elaborate synthetic techniques and tremendous effort. Especially, more than 10 synthetic steps are usually necessary to approach HBCs with lower symmetries. In order to simplify the synthetic work and reduce the high costs, a novel synthetic strategy involving only four steps was developed based on 2,3,5,6-tetraphenyl-1,4-diiodobenzene intermediates and palladium catalyzed Suzuki cross coupling reactions. In order to introduce various functionalities and expand the diversity of multi-functionalizations, a novel C2v-symmetric dihalo HBC building block 2-47, which contains one iodine and one bromine in para positions, was prepared following the traditional intermolecular [4+2] Diels-Alder reaction route. The outstanding chemical selectivity between iodo and bromo groups in this compound consequently leads to lots of HBC derivatives bearing different functionalities. Directly attached heteroatoms will improve the material properties. According to the application of intramolecular Scholl reaction to a para-dimethoxy HPB, which leads to a meta-dimethoxy HBC, a phenomenon of phenyl group migration was discovered. Thereby, several interesting mechanistic details involving arenium cation intermediates were discussed. With a series of dipole functionalized HBCs, the molecular dynamics of this kind of materials was studied in different phases by DSC, 2D WAXD, solid state NMR and dielectric spectroscopies. High charge carrier mobility is an important parameter for a semiconductive material and depends on the degree of intramolecular order of the discotic molecules in thin films for HBC derivatives. Dipole – dipole interaction and hydrogen bonds were respectively introduced in order to achieve highly ordered supramolecular structure. The self-assembly behavior of these materials were investigated both in solution and solid state. Depending upon the different functionalities, these novel materials show either gelating or non-linear optical properties, which consequently broaden their applications as functional materials. In the field of conceivable electronic devices at a molecular level, HBCs hold high promise. Differently functionalized HBCs have been used as active component in the studies of single-molecular CFET and metal-SAMs-metal junctions. The outstanding properties shown in these materials promise their exciting potential applications in molecular devices.

C 3-symmetric discotic liquid crystalline materials for molecular electronics: versatile synthesis and self-organization

This thesis presents the versatile synthesis and self-organization of C3-symmetric discotic nanographene molecules as well as their potential applications as materials in molecular electronics. The details can be described as follows: 1) A novel synthetic strategy towards properly designed C3 symmetric 1,3,5-tris-2’arylbenzene precursors has been developed. After the final planarization by treatment with FeCl3 under mild conditions, for the first time, it became possible to access a variety of new C3-symmetric hexa-peri-hexabenzocoronenes (HBCs) and a series of triangle-shaped nanographenes. D3 symmetric HBC with three alkyl substituents and C2 symmetric HBC with two alkyl substituents were synthesized and found to show the surprising decrease of isotropic points., the self-assembly at the liquid-solid interface displayed a unique zigzag and flower patterns. 2) Triangle-shaped discotics revealed a unique self-assembly behavior in solution, solid state as well as at the solution-substrate interface. A mesophase stability over the broad temperature range with helical supramoelcular arrangement were observed in the bulk state. The honeycomb pattern as the result of novel self-assembly was presented. Triangle-shaped discotics with swallow alkyl tails were fabricated into photovoltaic devices, the supramolecular arrangement upon thermal treatment was found to play a key role in the improvement of solar efficiency. 3) A novel class of C3 symmetric HBCs with alternating polar/apolar substituents was synthesized. Their peculiar self-assembly in solution, in the bulk and on the surface were investigated by NMR techniques, X-ray diffraction as well as different electron microscope techniques. 4) A novel concept for manipulating the intracolumnar stacking of discotics and thus for controlling the helical pitch was presented. A unique staggered stacking in the column was achieved for the first time. Theoretical simulations confirmed this self-organization and predicted that this packing should show the highest charge carrier mobility for all discotics.

Structure, organization and dynamics of functional supramolecular materials studied by solid-state NMR

Functional materials have great importance due to their many important applications. The characterization of supramolecular architectures which are held together by non-covalent interactions is of most importance to understand their properties. Solid-state NMR methods have recently been proven to be able to unravel such structure-property relations with the help of fast magic-angle spinning and advanced pulse sequences. The aim of the current work is to understand the structure and dynamics of functional supramolecular materials which are potentially important for fuel-cell (proton conducting membrane materials) and solar-cell or plastic-electronic applications (photo-reactive aromatic materials). In particular, hydrogen-bonding networks, local proton mobility, molecular packing arrangements, and local dynamics will be studied by the use of advanced solid-state NMR methods. The first class of materials studied in this work is proton conducting polymers which also form hydrogen-bonding network. Different materials, which are prepared for high 1H conduction by different approaches are studied: PAA-P4VP, PVPA-ABPBI, Tz5Si, and Triazole-functional systems. The materials are examples of the following major groups; - Homopolymers with specific functional groups (Triazole functional polysiloxanes). - Acid-base polymer blends approach (PAA-P4VP, PVPA-ABPBI). - Acid-base copolymer approach (Triazole-PVPA). - Acid doped polymers (Triazole functional polymer doped with H3PO4). Perylenebisimide (PBI) derivatives, a second type of important functional supramolecular materials with potent applications in plastic electronics, were also investigated by means of solid-state NMR. The preparation of conducting nanoscopic fibers based on the self-assembling functional units is an appealing aim as they may be incorporated in molecular electronic devices. In this category, perylene derivatives have attracted great attention due to their high charge carrier mobility. A detailed knowledge about their supramolecular structure and molecular dynamics is crucial for the understanding of their electronic properties. The aim is to understand the structure, dynamics and packing arrangements which lead to high electron conductivity in PBI derivatives.

Complex materials via colloidal crystallization

The work presented in this thesis deals with complex materials, which were obtained by self-assembly of monodisperse colloidal particles, also called colloidal crystallization. Two main fields of interest were investigated, the first dealing with the fabrication of colloidal monolayers and nanostructures, which derive there from. The second turned the focus on the phononic properties of colloidal particles, crystals, and glasses. For the fabrication of colloidal monolayers a method is introduced, which is based on the sparse distribution of dry colloidal particles on a parent substrate. In the ensuing floating step the colloidal monolayer assembles readily at the three-phase-contact line, giving a 2D hexagonally ordered film under the right conditions. The unique feature of this fabrication process is an anisotropic shrinkage, which occurs alongside with the floating step. This phenomenon is exploited for the tailored structuring of colloidal monolayers, leading to designed hetero-monolayers by inkjet printing. Furthermore, the mechanical stability of the floating monolayers allows the deposition on hydrophobic substrates, which enables the fabrication of ultraflat nanostructured surfaces. Densely packed arrays of crescent shaped nanoparticles have also been synthesized. It is possible to stack those arrays in a 3D manner allowing to mutually orientate the individual layers. In a step towards 3D mesoporous materials a methodology to synthesize hierarchically structured inverse opals is introduced. The deposition of colloidal particles in the free voids of a host inverse opal allows for the fabrication of composite inverse opals on two length scales. The phononic properties of colloidal crystals and films are characterized by Brillouin light scattering (BLS). At first the resonant modes of colloidal particles consisting of polystyrene, a copolymer of methylmethacrylate and butylacrylate, or of a silica core-PMMA shell topography are investigated, giving insight into their individual mechanical properties. The infiltration of colloidal films with an index matching liquid allows measuring the phonon dispersion relation. This leads to the assignment of band gaps to the material under investigation. Here, two band gaps could be found, one originating from the fcc order in the colloidal crystal (Bragg gap), the other stemming from the vibrational eigenmodes of the colloidal particles (hybridization gap).

Heusler compounds as thermoelectric materials

Heusler compounds as thermoelectric materialsrnrnThis work reports on Heusler and Half Heusler compounds and their thermoelectric properties. Several compounds were synthesized and their resistivity, Seebeck coefficient, thermal conductivity, and the figure of merit were determined. The results are presented in the following chapters.rnrnIn chapter 3 Co was substituted with Ni and Fe in the series TiCo1-x(Fe0.5Ni0.5)xSb. The substitution lead to a reduced loss of Sb during the synthesis. Further the Seebeck coefficient was increased and the thermal conductivity was reduced. These observations can be used to significantly improve the quality of TiCoSb based compounds in thermoelectric applications. rnrnIn chapter 4 the series TiCo1-xNixSnxSb1-x was investigated. Ni was substituted with Co and Sn with Sb. Especially for high Ni concentrations the figure of merit was enhanced compared to unsubstituted TiCoSb. This enhancement is based on the strong reduction of the thermal conductivity. The found values are among the lowest that have been determined up to date for Heusler compounds. rnrnIn chapter 5 Li containing Heusler compounds were theoretically and experimentally investigated. Li containing Heusler compounds are of special interest because the Li atoms scatter phonons efficiently. Therefore the thermal conductivity is decreased. The thermoelectric properties and especially the thermal conductivity are investigated in this chapter.rnrnIn chapter 6 several substitutions of TiCoSb were investigated. In the series TiCo1+xSb additional Co was introduced into the vacancies of the compound and the effect on the thermoelectric properties was measured. In the series TiCo1-xCuxSb Co was substituted with Cu. No significant enhancement of the ZT value were observed. In the series TiCoSb1-xBix Sb was substituted by Bi. The thermoelectric properties were significantly enhanced for small Bi concentrations. The Seebeck coefficient was increased and the resistivity was reduced at the same time. This unusual phenomenon is explained by band structure calculations.rnrnIn chapter 7 the material class of half metallic ferromagnets was investigated as a new materialclass for thermoelectric applications. The 26 valence electron compounds Co2TiSi, Co2TiGe, and Co2TiSn were used as model systems. The transport properties were determined theoretically. Then the properties were measured and compared to the calculated ones. The calculated values are in good agreement with the experimentally determined ones. The observed Seebeck coefficient has a big value and is nearly constant above the Curie temperature. This makes the materials appealing for the use as materials in thermocouples.rn