Visualization and study of reconformation of polyelectrolytes (PEs) of different architecture is of great fundamental and practical interest. Verification of theoretical predictions with experiment is of essential importance. On the other hand, a wide range of bottom-up techniques based on patterning of matter on the length scale of a few nanometers have been recently developed. Particularly interesting is the possibility of using self-assembled single molecule structures as templates for the deposition of inorganic matter, in particular metals. Synthetic "normal-sized" polymers of various architecture, like poly-2-vinylpyridine (P2VP) or polystyrene-poly(2-vynil pyridine) P2VP7-PS7 star-like block copolymer, adsorbed on solid substrates have been visualized for the first time with molecular resolution by AFM in different conformation. This finding allowed us to study largely discussed problem, a coil-to-globule transition of PEs. It was found that PE molecules undergo conformational transitions from stretched worm-like coil to compact globule via set of necklace-like globules, as the fraction of charged monomers decreases with an increase of pH and ionic strength. These results are in good agreement with recently developed DRO theory for weakly charged flexible PEs in poor solvent. The size of the deposited single molecules correlates very well with molecular dimensions in solution obtained in light scattering experiments. PE single molecules of various architectures was mineralized in different conformations that constitutes the route to nanoparticles with desired shape (including wire-shape and star-shaped), size, and composition (including metallic, magnetic and semiconductive nanoparticles). It was shown that molecular details of the adsorbed linear flexible PE molecules determine the dimensions of the nanostructures after metallization and that observed sizes are consistent with the decoration of single molecules with nanoclusters. Thus those metallized nanoparticles (cluster assembles) reflect the conformation of original adsorbed PE molecules. The dimensions of the obtained nanowires are significantly smaller than those previously reported. All of these features are of the potential benefit in applications for nanodevices. Metallization of the PS7-P2VP7 improves AFM resolution due to the selective deposition of Pd clusters along the P2VP chains. For the first time, the number of the P2VP second generation arms of the heteroarm block-copolymer was directly counted in the single molecule AFM experiment. Simple contrasting procedure was developed to improve AFM visualization of positively charged polymer chains deposited on the substrates of relatively high roughness. This method allows increasing the thickness of the resulting structures up to 10 nm, and, consequently, provide visualization of polymer chains on rough surfaces. This innovation is important for the development of single molecule experiments with polymer chains. The reaction of HCF-anion could be used for recognition of polycation molecules, when polycations, polyanions and neutral molecules coexist on the surface. Recently, the study was strongly restricted to atomically smooth surfaces. The contrasting procedure extends the range of substrates (Si-wafers, chemically modified or patterned Si-wafers, polished glasses, polymer films, etc) appropriate for the experiments. Thus, polymer single molecules can be considered not only as representative of the ensemble molecules, but also as individual nanoscale objects which can be used for future nanotechnology for the fabrication of single molecule electronic devices. Also these findings are important from fundamental point of view, since developed approach can be successfully applied for investigation of various "classical" problems in polymer science, such as polymer reconformation, interpolyelectrolyte complex formation, polymer diffusion, adsorption, etc.

Polycyclic nitrogen containing heterocycles form the basic skeleton of numerous alkaloids and physiologically active drugs. Alloyohimbane was obtained from 3,4-dihydro-â-carboline using an iron-mediated [2+2+1] cycloaddition as the key-step. The bis-TMS-diyne was conveniently obtained by the C-alkylation of 3,4-dihydro-â-carboline followed by N-alkylation. Demetalation of the iron-complex followed by hydrogenation, E-ring expansion, and reduction provided alloyohimbane, a structurally and biologically interesting substance, via a linear eight-step sequence in 7% overall yield based on 3,4-dihydro-â-carboline. Another sequence provided (±)-alloyohimbane and (±)-3-epi-alloyohimbane in nine steps. The pyrrole unit occurs in a variety of naturally occurring compounds, pharmaceutical products and polymers. A novel two-step procedure for the synthesis of pyrroles by addition of a propargyl Grignard reagent to a Schiff base and subsequent silver(I)-promoted oxidative cyclization of the resulting homopropargylamine has been developed. The generality of this reaction was proven by the synthesis of a broad variety of substituted pyrroles using silver(I)-promoted cyclization. A three-step synthesis of (±)-harmicine, a natural product isolated from the Malaysian plant Kopsia griffithii having strong anti-leishmania activity, from 3,4-dihydro-â-carboline is achieved by addition of 3-trimethylsilylpropargyl Grignard reagent, Ag(I)-promoted oxidative cyclization to a pyrrole, and chemoselective hydrogenation of pyrrole ring. Total synthesis of anti-tumor active crispine A and biologically active 1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinoline have been achieved in three steps using silver(I)-promoted oxidative cyclization as key step.

Oligomers and polymers based on functionalized Rf-amides were successfully synthesized for the fabrication of hydrophobic surfaces with either linear or network structure. Firstly, new functionalized Rf-amides (RfCONH-, Rf is a perfluoroalkyl segment) were developed in most cases by a one step reaction and a simple work-up procedure. The reaction behaviors of synthesized Rf-amides in polyreactions were well understood. New fluorinated oligoester polyols, blocked IPDI's, and end-hydroxyl terminated oligo(urea urethane)s have been synthesized, the detail structures and properties are well understood. These materials could be suitable components of powder coatings. On the other hand, the end-hydroxyl terminated oligo(urea urethane)s could be used as reactive additives in high solid content and water-borne coatings. Hydrophobic smooth surfaces based on linear polymers, poly(urea urethane)s and alternating MI copolymers, containing fluorinated side groups were successfully constructed. The attachment of fluorinated side groups into polymers can dramatically alter the surfaces of corresponding polymers from more hydrophilic to hydrophobic due to the enrichment of fluorinated side groups on the top of the surface. The backbone configuration, the polarity of backbones, and the thermal treatment on surfaces can influence the surface properties of corresponding materials. Finally, hydrophobic surfaces of cross-linked polyurethanes as model top coatings were constructed under melt condition at high temperature (180 and 190 oC) using the combination of fluorinated oligouretdiones and non-fluorinated oligoester polyols. It was found that the hydrophobicity of resulting cured films is a matter of the competition between the formation of cross-linking network and the segregation of fluoromoieties on the top of the surface.

Die Dissertation hat sich mit der Aufgabe befasst, durch Kombination von IR-Spektroskopie und chemometrischen Auswertungsalgorithmen eine Differenzierung und Klassifizierung von Hirnmetastasen-Dünnschnitten zu erreichen. Die Untersuchungen konzentrieren sich dabei auf jene fünf Primärtumoren, die besonders oft Metastasen im Gehirn bilden. Das sind kolorektale Karzinome, Mammakarzinome, maligne Melanome, Nierenzellkarzinome und Bronchialkarzinome. Metastasen tragen die molekularen Informationen der Gewebezellen des Primärtumors in sich. Die Anwendung von IR-spektroskopischen Methoden stellt deshalb einen innovativen Ansatz zur Identifikation des Primärtumors von Hirnmetastasen dar, da die Spektren einem molekularen Fingerabdruck entsprechen. Als Klassifizierungsalgorithmen wurden SIMCA (soft independent modeling of class analogies) und ANN (artificial neural networks) herangezogen. Die Entwicklung der Klassifizierungsverfahren gliederte sich in drei Teile. Im ersten Teil wurden Trainingsmodelle mit den ausgewählten homogenen Bereichen der Metastasengewebeschnitte erstellt und an unabhängigen Daten weiterer Proben bekannter und unbekannter Organherkunft getestet. Im zweiten Teil wurden die Modelle mit Hilfe homogener Tumorzelllinien optimiert und auf die Zuordnung der Hirnmetastasen zu den Primärtumoren angewandt. Eine zweistufige Klassifizierungsstrategie gewährleistet damit eine Genauigkeit der Klassifizierung von über 80%.

Abstract: When noble metals particles are synthesized with progressively smaller dimensions, strikingly novel optical properties arise. For nanoscale particles, collective disturbances of the electron density known as localized surface plasmons resonances can arise, and these resonances are utilized in a variety of applications ranging from surface-enhanced molecular spectroscopy and sensing to photothermal cancer therapy to plasmon-driven photochemistry. Central to all of these studies is the plasmon’s remarkable ability to process light, capturing and converting it into intense near fields, heat, and even energetic carriers at the nanoscale. In the past decade, we have witnessed major advances in plasmonics which is directly linked with the much broader field of (colloidal) nanotechnology. These breakthroughs span from plasmon lasing and waveguides, plasmonic photochemistry and solar cells to active plasmonics, plasmonics nanocomposites and semiconductor plasmons. All the above-mentioned phenomena rely on precise spatial placement and distinct control over the dimensions and orientation of the individual plasmonic building blocks within complex one-, two- or three-dimensional complex arrangements. For the nanofabrication of metal nanostructures at surfaces, most often lithographic approaches, e.g. e-beam lithography or ion-beam milling are generally applied, due to their versatility and precision. However, these techniques come along with several drawbacks such as limited scalability, limited resolution, limited compatibility with silicon manufacturing techniques, damping effects due to the polycrystalline nature of the metal nanostructures and low sample throughput. Thus, there is a great demand for alternative approaches for the fabrication of metal nanostructures to overcome the above-mentioned limitations. But why colloids? True three-dimensionality, lower damping, high quality modes due to mono-dispersity, and the absence of grain boundaries make the colloidal assembly an especially competitive method for high quality large-scale fabrication. On top of that, colloids provide a versatile platform in terms of size, shape, composition and surface modification and dispersion media. 540The combination of directed self-assembly and laser interference lithography is a versatile admixture of bottom-up and top-down approaches that represents a compelling alternative to commonly used nanofabrication methods. The objective of this thesis is to focus on large area fabrication of emergent spectroscopic properties with high structural and optical quality via colloidal self-assembly. We focus on synergy between optical and plasmonic effects such as: (i) coupling between localized surface plasmon resonance and Bragg diffraction leading to surface lattice resonance; (ii) strong light matter interaction between guided mode resonance and collective plasmonic chain modes leading to hybrid guided plasmon modes, which can further be used to boost the hot-electron efficiency in a semiconducting material; (iii) similarly, bilayer nanoparticle chains leading to chiro-optical effects. Following this scope, this thesis introduces a real-time tuning of such exclusive plasmonic-photonic (hybrid) modes via flexible template fabrication. Mechanical stimuli such as tensile strain facilitate the dynamic tuning of surface lattice resonance and chiro-optical effects respectively. This expands the scope to curb the rigidity in optical systems and ease the integration of such systems with flexible electronics or circuits.:Contents Abstract Kurzfassung Abbreviations 1. Introduction and scope of the thesis 1.1. Introduction 1.1.1. Classical optics concepts 1.1.2. Top down fabrication methods and their challenges 1.1.3. Template-assisted self-assembly 1.1.4. Functional colloidal surface assemblies 1.2. Scope of the thesis 2. Results and Discussion 2.1. Mechanotunable Surface Lattice Resonances in the Visible Optical Range by Soft Lithography Templates and Directed Self-Assembly 2.1.1. Fabrication of flexible 2D plasmonic lattice 2.1.2. Investigation of the influence of particle size distribution on SLR quality 2.1.3. Band diagram analysis of 2D plasmonic lattice 2.1.4. Strain induced tuning of SLR 2.1.5. SEM and force transfer analysis in 2D plasmonic lattice under various strain 2.2. Hybridized Guided-Mode Resonances via Colloidal Plasmonic Self-Assembled Grating 2.2.1. Fabrication of hybrid opto-plasmonic structure via template assisted self-assembly 2.2.2. Comparison of optical band diagram of three (plasmonic, photonic and hybrid) different structures in TE and TM modes 2.2.3. Simulative comparison of optical properties of hybrid opto-plasmonic NP chains with a grating of metallic gold bars 2.2.4. Effect of cover index variation with water as a cover medium 2.3. Hot electron generation via guided hybrid modes 2.3.1. Fabrication of the hybrid GMR structure via LIL and lift-off process 2.3.2. Spectroscopic and simulative analysis of hybrid opto-plasmonic structures of different periodicities 2.3.3. Comparative study of photocurrent generation in different plasmonic structures 2.3.4. Polarization dependent response at higher wavelength 2.3.5. Directed self-assembly of gold nanoparticles within grating channels of a dielectric GMR structure supported by titanium dioxide film 2.4. Active Chiral Plasmonics Based on Geometrical Reconfiguration 2.4.1. Chiral 3D assemblies by macroscopic stacking of achiral chain substrates 3. Conclusion 4. Zusammenfassung 5. Bibliography 6. Appendix 6.1. laser interference lithography 6.2. Soft molding 6.3. Determine fill factor of plasmonic lattice 6.4. 2D plasmonic lattice of Au_BSA under strain 6.5. Characterizing order inside a 2D lattice 6.6. Template-assisted colloidal self-assembly 6.7. Out of plane lattice resonance in 1D and 2D lattices 6.8. E-Field distribution at out of plane SLR mode for 1D lattices of various periodicity with AOI 20° 6.9. Refractive index of PDMS and UV-PDMS 6.10. Refractive index measurement for sensing 6.11. Optical constants of TiO2, ma-N 405 photoresist and glass substrate measured from spectroscopic ellipsometry Acknowledgement/ Danksagung Erklärung & Versicherung List of Publications

The present study focuses on the development of Al-based systems and their examination as a medium for reversible hydrogen uptake. The first part of this thesis is dedicated to the chemistry and properties of Al-N-based materials. The synthesis, characterization, and detailed thermal decomposition studies of several aminoalanes have been described. As a result, single-crystal X-ray diffraction analyses revealed two new crystal structures of piperidinoalanes. The perspective approach employing activated aluminum and piperidine for reversible hydrogen uptake has been established. The second part of this work was focused on the modification of the properties of NaAlH4-based systems in order to generate the material with the high dissociation pressure suitable for high-pressure tank technologies. Considerable progress has been achieved in improving the hydrogen sorption properties by adding the extra aluminum powder to the Ti-catalysed NaAlH4-based system. Thus, the present study contributes to the understanding of the hydrogen sorption behavior of Al-based systems with perspectives being applicable to other related materials.:DECLARATION ACKNOWLEDGEMENTS DEFINITIONS AND ABBREVIATIONS ABSTRACT CONTENTS LIST OF TABLES LIST OF FIGURES MOTIVATION AND GOALS 1 INTRODUCTION 1.1 The prospects for hydrogen-based energy systems 1.2 Requirements for the hydrogen storage system 1.3 An overview of hydrogen storage strategies 1.4 Complex hydrides as a promising hydrogen storage materials 1.4.1 Metal borohydride systems 1.4.2 Alanate-based systems 1.4.3 Nitrogen-containing complex hydrides 1.5 Summary 2 GENERAL CHARACTERIZATION METHODS 2.1 X-ray crystallography 2.1.1 X-ray powder diffraction (XRPD) 2.1.2 Single-crystal structure analysis 2.2 Thermal analysis 2.3 Quantitative chemical analysis 2.3.1 Elemental analysis 2.3.2 Inductively coupled plasma optical emission spectrometry (ICP-OES) 2.4 Nuclear magnetic resonance spectroscopy (NMR) 3 LIQUID-STATE HYDROGEN STORAGE 3.1 State of the art 3.1.1 Liquid-state hydrogen storage materials 3.1.2 Al-N-based compounds as potential materials for hydrogen storage 3.1.3 Summary 3.2 Materials preparation and experimental details 3.2.1 Chemicals and sample handling 3.2.2 Synthesis of aminoalane in diethyl ether solution with aluminum hydride 3.2.3 Preparation of activated aluminum 3.2.4 Direct hydrogenation of activated aluminum supported by amine 3.3 Results and discussion 3.3.1 Is the solid-state hydrogen storage in aminoalanes possible? 3.3.2 Optimization of the direct hydrogenation of activated aluminum supported by amine 3.3.2.1 Synthesis and characterization of triethylenediamine alane complex 3.3.2.2 Synthesis of aminoalanes via direct hydrogenation of activated aluminum and N-heterocyclic amine 3.3.3 Investigation of piperidinoalanes for reversible hydrogen uptake 3.3.3.1 Crystal structure determination of piperidinoalanes 3.3.3.2 Influence of the initial reaction parameters on the piperidinoalane formation 3.3.3.3 Reversible hydrogenation in piperidinoalane system 3.3.4 Conclusions 4 SOLID-STATE HYDROGEN STORAGE 4.1 State of the art 4.1.1 Thermodynamic tuning of the hydrides 4.1.2 Features of the sodium alanate system 4.1.3 Catalytic enhancement of reversible hydrogenation in sodium alanate 4.1.4 The relevance of the Al-TM species in doped sodium alanate 4.1.5 Summary 4.2 Materials preparation and experimental details 4.2.1 Chemicals and purification procedure 4.2.2 Activation procedure of sodium alanate via mechanochemical treatment 4.2.3 Pressure-composition-isotherm measurements with a Sieverts-apparatus 4.2.4 High-pressure differential scanning calorimetry investigation of sodium alanate samples 4.3 Results and discussion 4.3.1 Tailoring the properties of sodium alanate-based system with the help of Ti-additive 4.3.2 Influence of the aluminum addition on the sorption behavior of Ti-doped sodium alanate 4.3.3 High-pressure DSC study of hydrogen sorption properties of doped sodium alanate system 4.3.4 Conclusions 5 SUMMARY AND CONCLUSIONS RECOMMENDATIONS AND OUTLOOK REFERENCES SUPPORTING INFORMATION Appendix A Appendix B Appendix C Publications

A series of new 9,9‐diethylfluorenes consisting of three side‐arms each bearing a heterocyclic, bis(carboxymethyl)amino, bis(carbamoylmethyl)amino, bis(ethoxycarbonylmethyl)amino or an amino group were prepared on the basis of 2,4,7‐tris(bromomethyl)‐9,9‐diethylfluorene. Imidazolyl, benzimidazolyl, pyrazolyl, pyrrolyl, 1,3‐dioxoisoindolyl and pyridinium groups were taken into account as heterocyclic units, attached to the aromatic skeleton via −CH2−, −CH2NHCH2− or −CH2N=CH− linkers. In addition to the seventeen 2,4,7‐trisubstituted 9,9‐diethylfluorenes, two macrocyclic compounds were prepared on the basis of 2,7‐bis(aminomethyl)‐9,9‐diethylfluorene. The excellent yield of the macrocyclization reaction is worth a special mention. Both the acyclic and the macrocyclic fluorene‐based compounds have, among other things, the potential to act as artificial receptors for different substrates in analogy to the known receptors consisting of a benzene or biphenyl core.

Structurally well-defined graphene nanoribbons (GNRs) have emerged as highly promising materials for the next-generation nanoelectronics. The electronic properties of GNRs critically depend on their edge topologies. Here, we demonstrate the efficient synthesis of a curved GNR (cGNR) with a combined cove, zigzag, and armchair edge structure, through bottom-up synthesis. The curvature of the cGNR is elucidated by the corresponding model compounds tetrabenzo[a,cd,j,lm]perylene (1) and diphenanthrene-fused tetrabenzo[a,cd,j,lm]perylene (2), the structures of which are unambiguously confirmed by the X-ray single-crystal analysis. The resultant multi-edged cGNR exhibits a well-resolved absorption at the near-infrared (NIR) region with a maximum peak at 850 nm, corresponding to a narrow optical energy gap of ∼1.22 eV. Employing THz spectroscopy, we disclose a long scattering time of ∼60 fs, corresponding to a record intrinsic charge carrier mobility of ∼600 cm2 V–1 s–1 for photogenerated charge carriers in cGNR.

Two-dimensional conjugated covalent organic frameworks (2D c-COFs) are emerging as a unique class of semiconducting 2D conjugated polymers for (opto)electronics and energy storage. Doping is one of the common, reliable strategies to control the charge carrier transport properties, but the precise mechanism underlying COF doping has remained largely unexplored. Here we demonstrate molecular iodine doping of a metal–phthalocyanine-based pyrazine-linked 2D c-COF. The resultant 2D c-COF ZnPc-pz-I2 maintains its structural integrity and displays enhanced conductivity by 3 orders of magnitude, which is the result of elevated carrier concentrations. Remarkably, Hall effect measurements reveal enhanced carrier mobility reaching ∼22 cm2 V–1 s–1 for ZnPc-pz-I2, which represents a record value for 2D c-COFs in both the direct-current and alternating-current limits. This unique transport phenomenon with largely increased mobility upon doping can be traced to increased scattering time for free charge carriers, indicating that scattering mechanisms limiting the mobility are mitigated by doping. Our work provides a guideline on how to assess doping effects in COFs and highlights the potential of 2D c-COFs to display high conductivities and mobilities toward novel (opto)electronic devices.

In der vorliegenden Arbeit werden eine neue mikrowellenassistierte Darstellungsmethode für Bismutvanadatnanopartikel ebenso wie ein ultraschallgestütztes Sprühverfahren zur Abscheidung von Bismut(III)-oxidschichten beschrieben. Nanopartikuläres m-BiVO4 wird durch die Umsetzung von Bi(OtBu)3 mit VO(OtBu)3 unter Zugabe von polymersierbaren Alkoholen, nicht polymerisierbaren Alkoholen sowie ohne Zusätze in einer nichtwässrigen Lösung gefolgt von einer thermischen Oxidation erhalten. Anschließend werden die Nanopartikel hinsichtlich ihrer Eigenschaften verglichen. Ausgehend von einem polynuklearen Bismutoxidocluster wird über ultraschallgestütztes Kaltsprühen, einer sich anschließenden kontrollierten Hydrolyse und einer finalen thermischen Behandlung die Beschichtung verschiedener Substrate mit α-Bi2O3, β-Bi2O3 sowie α/β-Bi2O3 erreicht. Die Charakterisierung der synthetisierten Materialien erfolgt unter anderem mittels Pulverröntgendiffraktometrie, NMR-Spektroskopie, CHN-Analysen, UV/VIS-, IR- und Ramanspektroskopie, thermogravimetrischen Analysen sowie elektronenmikrospische Aufnahmen. Zusätzlich werden die Halbleiterschichten mit einer Wirbelstromsonde vermessen. Die bismuthaltigen Halbleitermaterialien sind im sichtbaren Lichtspektrum anregbar und weisen eine hohe photokatalytische Aktivität beim Abbau von Rhodamin B auf, wobei die zugrunde liegenden Abbaumechanismen UV/VIS-spektroskopisch aufgeklärt werden. Darüber hinaus werden die Photokatalysatoraktivitäten gegenüber wässrigen Lösungen von Methylorange, Orange G, Methylenblau sowie Schadstofflösungen des Biozids Triclosan und des pharmazeutischen Wirkstoffs Ethinylestradiol diskutiert, deren photokatalytische Zersetzung ergänzend mit TOC-Analysen verfolgt wird.:Abkürzungsverzeichnis.....11 1 Einleitung und Motivation.....15 2 Grundlagen der Photokatalyse.....21 2.1 Photokatalyse mit Halbleitern.....21 2.1.1 Definition und Unterteilung von Photokatalysatoren.....21 2.1.2 Funktionsweise, Eigenschaften und weitere Anwendungsfelder von Halbleiterphotokatalysatoren.....22 2.1.3 Cokatalysatoren in der Photokatalyse.....26 2.1.4 Photokatalysatoren mit Heteroübergang.....28 2.2 Photokatalytischer Abbau von organischen Substanzen.....29 2.2.1 Grundlagen zu Reaktionspfaden und aktiven Spezies.....29 2.2.2 Mechanismen und Kinetik der photokatalytischen Zersetzung am Beispiel von Rhodamin B.....32 2.3 Bismutvanadat als Photokatalysator.....38 2.4 Bismut(III)-oxid als Photokatalysator.....41 3 Photokatalytische Untersuchungen an Bismutvanadatnanopartikeln aus mikrowellenassistierten Synthesen.....47 3.1 Synthesemethoden für Metalloxidnanostrukturen und Voruntersuchungen zur nichtwässrigen Darstellung von nanoskaligem Bismutvanadat.....47 3.2 Darstellung von Bismutvanadatnanopartikeln über die Umsetzung von Bismut(III)-alkoxiden und Vanadium(V)-alkoxiden im Mikrowellenreaktor.....53 3.2.1 Umsetzung von Bismut(III)-alkoxiden und Vanadium(V)-alkoxiden im Mikrowellenreaktor.....53 3.2.2 Darstellung von Bismutvanadatnanopartikeln durch thermische Oxidation der Materialien MW-II – MW-V.....57 3.3 Photokatalytische Untersuchungen an monoklinen Bismutvanadatnanopartikeln .....61 3.3.1 Untersuchungen zu den photoinduzierten Abbaumechanismen von Rhodamin B mit Bismutvanadatnanopartikeln.....61 3.3.2 Vergleich der photokatalytischen Aktivität von BiVO4-II – BiVO4-V und photokatalytische Untersuchungen zum Abbau weiterer Farbstoffe.....65 4 Photokatalytische Untersuchungen an Bismut(III)-oxidschichten aus einem ultraschallgestützten Sprühverfahren.....72 4.1 Darstellungsmethoden für β-Bismut(III)-oxidschichten.....72 4.2 Darstellung, Modifizierung und photokatalytische Untersuchungen von α- und β- Bismut(III)-oxidschichten aus einem ultraschallgestützten Sprühverfahren.....76 4.2.1 Darstellung von α- und β-Bismut(III)-oxidschichten über ein ultraschallgestütztes Sprühverfahren ausgehend von [Bi38O45(OMc)24(DMSO)9]·2DMSO·7H2O und deren photokatalytische Untersuchung.....76 4.2.2 Modifizierung der Präparationsmethode und die photokatalytische Zersetzung von Schadstoffen mit optimierten β-Bismut(III)-oxidschichten.....84 4.2.3 Darstellung von Au/β-Bismut(III)-oxidschichten und deren photokatalytische Untersuchung.....94 4.3 Darstellung und photokatalytische Untersuchungen von α/β-Bismut(III)- oxidschichten aus einem ultraschallgestützten Sprühverfahren.....99 4.3.1 Darstellung von α/β-Bismut(III)-oxidschichten über ein ultraschallgestütztes Sprühverfahren ausgehend von [Bi38O45(OMc)24(DMSO)9]·2DMSO·7H2O.....99 4.3.2 Photokatalytische Untersuchungen an α/β-Bismut(III)-oxidschichten.....104 5 Zusammenfassung und Ausblick.....108 6 Experimenteller Teil.....116 6.1 Eingesetzte Chemikalien und Arbeitstechniken.....116 6.2 Verwendete Gerätetechnik.....116 6.3 Umsetzungen von Alkoxiden und Chloriden des Bismut(III) und Vanadium(V) mit und ohne Zusatz von Alkoholen.....122 6.3.1 Umsetzung von Bi(OtBu)3 und VO(OtBu)3 in Benzylalkohol unter Rückfluss (RF-I).....122 6.3.2 Umsetzung von BiCl3 und VOCl3 in Benzylalkohol unter Rückfluss (RF-II)..123 6.3.3 Umsetzung von Bi(OtBu)3 und VO(OtBu)3 in Benzylalkohol im Mikrowellenreaktor (MW-I).....123 6.3.4 Umsetzung von Bi(OtBu)3, VO(OtBu)3 und 2-Methoxybenzylalkohol im Mikrowellenreaktor (MW-II).....123 6.3.5 Umsetzung von Bi(OtBu)3, VO(OtBu)3 und 2,4-Dimethoxybenzylalkohol im Mikrowellenreaktor (MW-III).....124 6.3.6 Umsetzung von Bi(OtBu)3, VO(OtBu)3 und 2-(Thiophen-2-yl)propan-2-ol im Mikrowellenreaktor (MW-IV).....124 6.3.7 Umsetzung von Bi(OtBu)3 und VO(OtBu)3 im Mikrowellenreaktor (MW-V)...125 6.4 Darstellung von BiVO4 durch thermische Oxidation der Materialien MW-II – MW-V.....125 6.5 Darstellung der Bismut(III)-oxidschichten über ein ultraschallgestütztes Sprühverfahren.....126 6.5.1 β-Bi2O3-Schichten ausgehend von [Bi38O45(OMc)24(DMSO)9]·2DMSO·7H2O.....126 6.5.2 α-Bi2O3-Schichten ausgehend von [Bi38O45(OMc)24(DMSO)9]·2DMSO·7H2O.....127 6.5.3 Au/β-Bi2O3-Schichten ausgehend von β-Bi2O3-Schichten mittels Photodeposition.....127 6.5.4 α/β-Bi2O3-Schichten ausgehend von [Bi38O45(OMc)24(DMSO)9]·2DMSO·7H2O.....128 6.6 Photokatalytische Untersuchungen.....128 7 Literaturverzeichnis.....131 8 Anhang.....159 Curriculum Vitae.....177 Publikationsverzeichnis.....178 Tagungsbeiträge.....179 Selbstständigkeitserklärung.....181