Small molecule Zn(II) complexes containing N- and S- donor environments may serve as appropriate models for mimicking Zn protein sites, and thus, their reactions with heavy metal ions such as Pt(II) and W(0) may provide insight into possible adduct formation and zinc displacement. To study such possible interactions between zinc finger proteins and platinum-bound DNA, the ZnN2S2 dimeric complex, N,N?-bis(2- mercaptoethyl)-1,4-diazacycloheptane zinc (II), [Zn-1?]2, has been examined for Znbound thiolate reactivity in the presence of Pt(II) nitrogen ? rich compounds. The reactions yielded Zn/Pt di- and tri- nuclear thiolate-bridged adducts and metalexchanged products, which were initially observed via ESI-mass spectrometry (ESI-MS) analysis of reaction solutions, and ultimately verified by comparison to the ESI-MS analysis, 195Pt NMR spectroscopy, and X-ray crystallography of directly synthesized complexes. The isolation of Zn-(?-SR)-Pt-bridged [(Zn(bme-dach)Cl)(Pt(dien))]Cl adduct from these studies is, to our knowledge, the first Zn-Pt bimetallic thiolatebridged model demonstrating the interaction between Zn-bound thiolates and Pt(II). Additional derivatives involving Pd(II) and Au(III) have been explored to parallel the experiments executed with Pt(II). The [Zn-1?]2 was then modified by cleavage with Na+[ICH2CO2]- to produce (N- (3-Thiabutyl)-N?-(3-thiapentaneoate)-1,4-diazacycloheptane) zinc(II), Zn-1?-Ac or ZnN2SS?O, and 1,4-diazacycloheptane-1,4-diylbis(3-thiapentanoato) zinc(II), Zn-1?-Ac2 or ZnN2S?2O2, monomeric complexes (where S = thiolate, S? = thioether). The [Zn-1?]2 di- and Zn-1?-Ac mono-thiolato complexes demonstrated reactivity towards labile-ligand tungsten carbonyl species, (THF)W(CO)5 and (pip)2W(CO)4, to yield, respectively, the [(Zn-1?-Cl)W(CO)4]- complex and the [(Zn-1?-Ac)W(CO)5]x coordination polymer. With the aid of CO ligands for IR spectral monitoring, the products were isolated and characterized spectroscopically, as well as by X-ray diffraction and elemental analysis. To examine the potential for zinc complexes (or zinc-templated ligands) to possibly serve as a toxic metal remediation agents, Zn-1?-Ac and Zn-1?-Ac2 were reacted with Ni(BF4)2. The formation of Zn/Ni exchanged products confirmed the capability of ?free? Ni(II) to displace Zn(II) within the N-, S-, and O- chelate environment. The Zn/Ni exchanged complexes were analyzed by ESI-MS, UV-visible spectroscopy, IR spectroscopy of the acetate regions, and X-ray crystallography. They serve as foundation molecules for more noxious metal exchange / zinc displacement products.

Chemical biology encompasses the study and manipulation of biological system using chemistry, often by virtue of small molecules or unnatural amino acids. Much insight has been gained into the mechanisms of biological processes with regards to protein structure and function, metabolic processes and changes between healthy and diseased states. As an ever expanding field, developing new tools to interact with and impact biological systems is an extremely valuable goal. Herein, work is described towards the synthesis of a small library of heterocyclic-containing small molecules and the mechanistic details regarding the interesting and unexpected chemical compounds that arose; an alternative set of non-toxic copper catalyzed azide-alkyne click conditions for in vivo metabolic labelling; and the synthesis of an unnatural amino acid for further chemical modification via [3+2] cycloadditions with nitrones upon incorporation into a peptide of interest. Altogether, these projects strive to supplement pre-existing methodology for the synthesis of small molecule libraries and tools for metabolic labelling, and thus provide further small molecules for understanding biological systems.

LKB1 is the second most commonly altered tumour suppressor gene in lung adenocarcinoma, the most prevalent form of lung cancer. LKB1 is a "master kinase" that has been shown to phosphorylate up to 13 downstream targets. We hypothesised that LKB1 loss is associated with an increased dependency on alternative, targetable pathways. The overall aims of this project were to better understand the role of LKB1 loss in lung cancer and to identify novel approaches to selectively target LKB1 mutated cells. We generated isogenic cells with or without LKB1 and used these to study the effect of LKB1 on cell proliferation. Importantly, we used a range of models including 2D culture, 3D spheroids and, sub-cutaneous and orthotopic xenograft models. To understand the role of LKB1 loss in lung cancer, the effect of LKB1 on mRNA expression was analysed using whole genome RNA Sequencing. To identify novel approaches to selectively target LKB1 mutated cells, we used biological screening methods and also investigated the effect of several metabolic inhibitors. We found that loss of LKB1 expression had no effect on cell proliferation in 2D culture, but was associated with increased growth in 3D spheroids, sub-cutaneous and orthotopic xenografts, as well as greater metastasis in a lung orthotopic model. Gene ontology analysis of the transcriptome identified that genes associated with cAMP signalling and cytoskeletal organisation were differentially expressed between LKB1 deficient and proficient cells. We confirmed that cAMP signalling was increased in LKB1 deficient cells, though there was no difference in sensitivity between LKB1 deficient and proficient cells to cAMP signalling modulators. The bioactive small molecule screen showed that LKB1 deficient cells underwent apoptosis more slowly and therefore, were less sensitive to many compounds, compared with LKB1 proficient cells. Screening in 3D spheroids was a novel approach that we used to identify microtubule inhibitors as potentially selective compounds acting in LKB1 deficient cells. Our RNASeq data suggests that there was a metabolic shift from oxidative phosphorylation to aerobic glycolysis in LKB1 deficient cells, although this did not affect sensitivity to complex I inhibitors. Importantly, LKB1 deficient cells were more sensitive to glucose and glutamine deprivation which suggests that targeting these metabolic pathways may hold the greatest promise to selectively inhibit proliferation in LKB1 mutated cells.

This thesis describes a structure activity relationship (SAR) study on the recently discovered small molecule tool blebbistatin (S)-21 with particular emphasis on the development of novel synthetic protocols suitable for the rapid synthesis of libraries of blebbistatin analogues. These analogues are potentially of use as novel myosin inhibitors Chapter 1 introduces the concept of chemical biology with particular emphasis on chemical genetics. This approach has rekindled the search for new chemical tools for the investigation of biological systems. The success of blebbistatin (S)-21, which was identified in a chemical genetic study, as a research tool was also discussed. The link between several myosin classes and genetic diseases such as coeliac disease, Crohn’s disease, deafness, dermatitis, familial hypertrophic cardiomyopathy, Griscelli disease and ulcerative colitis indicate that potent inhibitors which show selectivity towards specific myosin isoforms may be of great value as tools for the study of these conditions. The plan for the SAR study around (S)-21 was outlined. Chapter 2 describes the studies undertaken to develop an efficient synthetic route to N1-alkyl analogues of (S)-21 suitable for the parallel synthesis of chemical collections. These studies culminated in the synthesis of an intermediate (S)-66 from which novel N1-alkyl analogues were synthesised. The biological evaluation of these N1-alkyl analogues was discussed. Chapter 3 describes the development of a protocol suitable for the parallel synthesis of collections of N1-aryl analogues of (S)-21 via the intermediate 66. The application of this protocol to the synthesis of a collection of racemic N1-aryl and heteroaryl analogues of (S)-21 and their biological evaluation was presented. Chapter 4 describes the successful rational design and synthesis of a novel fused thiophene ring containing inhibitor of myosin II. The structure of this compound was proposed by modelling of the existing co-crystal structure of (S)-21 bound to the metastable state of Dictyostelium discoideum myosin II (S1dC) and sought to optimise the π-π stacking interaction displayed by (S)-21 with the tyrosine 261 residue within its binding site. The biological evaluation of this novel analogue was discussed. In Chapter 5 the studies conducted to investigate the contribution of ring-C to the binding affinity of (S)-21 were described. The development of alternate routes to (S)-21, in an attempt to avoid difficulties experienced during the synthesis of some analogues of (S)-21, are described. The synthesis and biological investigation of the fluorescent dye PPBA whose binding site has been suggested to overlap with that of (S)-21 was also reported.

abstract: Detection of molecular interactions is critical for understanding many biological processes, for detecting disease biomarkers, and for screening drug candidates. Fluorescence-based approach can be problematic, especially when applied to the detection of small molecules. Various label-free techniques, such as surface plasmon resonance technique are sensitive to mass, making it extremely challenging to detect small molecules. In this thesis, novel detection methods for molecular interactions are described. First, a simple detection paradigm based on reflectance interferometry is developed. This method is simple, low cost and can be easily applied for protein array detection. Second, a label-free charge sensitive optical detection (CSOD) technique is developed for detecting of both large and small molecules. The technique is based on that most molecules relevant to biomedical research and applications are charged or partially charged. An optical fiber is dipped into the well of a microplate. It detects the surface charge of the fiber, which does not decrease with the size (mass) of the molecule, making it particularly attractive for studying small molecules. Third, a method for mechanically amplification detection of molecular interactions (MADMI) is developed. It provides quantitative analysis of small molecules interaction with membrane proteins in intact cells. The interactions are monitored by detecting a mechanical deformation in the membrane induced by the molecular interactions. With this novel method small molecules and membrane proteins interaction in the intact cells can be detected. This new paradigm provides mechanical amplification of small interaction signals, allowing us to measure the binding kinetics of both large and small molecules with membrane proteins, and to analyze heterogeneous nature of the binding kinetics between different cells, and different regions of a single cell. Last, by tracking the cell membrane edge deformation, binding caused downstream event – granule secretory has been measured. This method focuses on the plasma membrane change when granules fuse with the cell. The fusion of granules increases the plasma membrane area and thus the cell edge expands. The expansion is localized at the vesicle release location. Granule size was calculated based on measured edge expansion. The membrane deformation due to the granule release is real-time monitored by this method. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2015

As estruturas cristalinas dos complexos Ln(ClO4)3.6[PONH2(C6H5)2] onde Ln=Eu, La, Cu[NH2(CH3)2CCO2]2, NiBr2.4[AsO(C6H5)3].8H2O (verde) e NiBr2.4[AsO(C6H5)3].1,5(CH3C6H5).H2O (alaranjado) bem como do ligante PONH2(C6H5)2 foram determinadas por difração de raios-X. Os complexos envolvendo íons lantanídeos refinaram a fatores R finais de R(Eu)=0,125, e R(La)=0,133 e foram encontradas a seguintes características principais: a) o sistema cristalino é cúbico; b) a coordenação do cátion é feita por seis átomos de oxigênio dos ligantes em configuração octaédrica (Eu) e antiprismática trigonal (La) com as terras raras em posições de alta simetria (23 para Eu e 3 para La); c) o restante das estruturas apresentam diferentes graus de desordem. À luz da sua configuração geométrica, a presença de uma forte banda 5Do-7F2 no espectro de fluorescência do complexo de Eu, proibida por considerações de simetria, é explicada como decorrente de acoplamentos vibrônicos. O desdobramento da linha υP=0 do espectro de infravermelho do coplxo de La é atribuído à presença de grupos P=0 não equivalentemente ligados a terra rara devido à desordem desta. O composto envolvendo o íon Cu(II) (fator R final 0,053) cristaliza no sistema monoclínico com os complexos se empacotando em camadas paralelas ao plano cristalino (100) com redes de pontes de H intracamada e com francas interações entre camadas consecutivas, o que explica o comportamento magnético quasi-bidimensional observado nestes cristais. O complexo de Ni(II) de coloração verde (fator R final 0,039) apresenta o íon metálico sobre um centro de simetria coordenado por seis moléculas de água numa conformação octaédrica distorcida, as quais estão ligadas aos grupos tfaso[AsO(C6H5)3] e íons brometo por fatores pontes de H. No complexo de coloração alaranjada (fator R final 0,087) o cátion está pentacoordenado com os quatro oxigênios dos ligantes tfaso formando a base de uma pirâmide quadrangular e um ânion Br- ocupando a quinta posição. Como uma conseqüência da resolução e refinamento da estrutura do complexo de Eu, a estrutura cristalina do ligante PONH2(C6H5) puro foi também determinada e refinada a um fator R de 0,033. / The crystal structure of the complexes Ln(ClO4)3.6[PONH2(C6H5)2] where Ln=Eu, La, Cu[NH2(CH3)2CCO2]2, NiBr2.4[AsO(C6H5)3].8H2O (green), NiBr2.4[AsO(C6H5)3.1,5(CH3C6H5).H2O (orange) and of the ligand PONH2(C6H5)2 have been determined by X-ray diffraction. The complexes involving lanthanide ions refined to final R factors of R(Eu)=0.125 and R(La)=0.133 and the following main features were found: a) the crystal system is cubic; b) the cation is coordinated to six ligand oxygens in octahedral earths on position of high symmetry (23 for Eu and 3 for La); c) the rest of the structures shows different degrees of disorder. In the light of the geometrical configuration, the occurrence of a strong band 5Do-7F2 in the fluorescence spectrum of the Eu complex, forbidden on symmetry grounds, is interpreted as a consequence of vibronic coupling. A splitting of the infrared υP=0 band in the La complex is attributed to the presence of P=0 goups non-equivalently bonded to the rare earth due to the disorder of this atom. The compound involving the Cu(II) ion (final R factor of 0.053) crystallizes in the monoclinic system with the complexes packed in layers parallel to the (100) crystal plane, with intralayer nets of H bonds and weak interactions between consecutive layers, which explains the quasi two-dimensional magnetic behavior observed in these crystals. In the green Ni(II) complex (final R=0.039), the metallic ion is sited on a center of symmetry and is octahedrally coordinated to six water molecules which are hydrogen bonded to the tfaso[AsO(C6H5)3] groups and the bromide ions. In the orange complex (final R=0.087) the cation is pentacoordinated with the four oxygens of the tpas ligands forming the basis of a quadrangular pyramid and one Br- anion in the fifth position. As a by product in the solution and refinement of the Eu complex structure, the crystal structure of the pure ligand PONH2(C6H5) was also determined and refined to a R-factor of 0.033.

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Chemical biology encompasses the study and manipulation of biological system using chemistry, often by virtue of small molecules or unnatural amino acids. Much insight has been gained into the mechanisms of biological processes with regards to protein structure and function, metabolic processes and changes between healthy and diseased states. As an ever expanding field, developing new tools to interact with and impact biological systems is an extremely valuable goal. Herein, work is described towards the synthesis of a small library of heterocyclic-containing small molecules and the mechanistic details regarding the interesting and unexpected chemical compounds that arose; an alternative set of non-toxic copper catalyzed azide-alkyne click conditions for in vivo metabolic labelling; and the synthesis of an unnatural amino acid for further chemical modification via [3+2] cycloadditions with nitrones upon incorporation into a peptide of interest. Altogether, these projects strive to supplement pre-existing methodology for the synthesis of small molecule libraries and tools for metabolic labelling, and thus provide further small molecules for understanding biological systems.

In the first part of this work, a convenient and high yielding synthetic strategy was developed to approach highly electrophilic fluorophosphonium cations as triflate salts. Through in situ electrophilic fluorination of phosphanes with commercially available bench-stable N-fluorobenzenesulfonimide (NFSI), followed by subsequent methylation of the [N(PhSO2)2]- anion with MeOTf, a library of mono-, di- and tri- cationic fluorophosphonium triflates were obtained in excellent yields. The Lewis acidities of all synthesized fluorophosphonium triflates salts were evaluated by both theoretical and experimental methods. These fluorophosphonium triflates have been develop as catalysts for the conversation of formamides into N-sulfonyl formamidines. CHAPTER II of this work focus on developing electrophilic fluorophosphonium cation as Lewis acid pedant in both inter- and intra- molecular FLP systems, as well as exploring their application in small molecular activation and functionalization, such as reversible CO2 sequestration and binding of carbonyls, nitriles and acetylenes. CHAPTER III of this thesis reports on the reaction of electrophilic fluorophosphonium triflates with trimethylsilyl nucleophiles (Me3SiX, X = CN, N3), which selectively yields either pseudohalo-substituted flurophosphoranes or pseudohalo-substituted phosphonium cations.:1. Introduction 1 1.1. Frustrated Lewis Pair chemistry 2 1.2. Phosphorus derivatives as strong Lewis acids 6 2. Objective 11 3. CHAPTER I: Synthesis of fluorophosphonium triflate salts and application as catalyst 15 3.1. Electrophilic fluorination of phosphanes: a convenient approach to electrophilic fluorophosphonium cations 15 3.2. Fluorophilicities and Lewis acidities of the obtained fluorophosphonium derivatives 23 3.2.1. Evaluation of fluorophilicities and Lewis acidities of the obtained fluorophosphonium cations 24 3.2.2. Reactions of fluorophosphonium salts with selected formamides. 27 3.2.3. Reactions of fluorophosphonium salts with selected urea derivatives 31 3.3. Transformation of formamides to N-sulfonyl formamidines using fluorophosphonium triflates as active catalysts 34 4. CHAPTER II: Bifunctional electrophilic fluorophosphonium triflates as intramolecular Frustrated Lewis Pairs 45 5. CHAPTER III: Reaction of fluorophosphonium triflate salts with trimethylsilyl nucleophiles 63 6. Summary 73 7. Perspective 77 8. Experimental section 80 8.1. Materials and methods 80 8.2. Experimental details for CHAPTER I 82 8.2.1. Preparation of imidazoliumyl-substituted phosphanes. 82 8.2.1.1. Preparation of [Ph2LcMeP][OTf] 82 8.2.1.2. Preparation of [Ph2LciPrP][OTf] 83 8.2.1.3. Preparation of [(C6F5)2LcMeP][OTf] 83 8.2.1.4. Preparation of [(C6F5)2LciPrP][OTf] 84 8.2.1.5. Preparation of [PhLcMe2P][OTf]2 85 8.2.1.6. Preparation of [PhLciPr2P][OTf]2 85 8.2.2. Preparation of fluorophosphonium bis(phenylsulfonyl)amide salts 86 8.2.2.1. Preparation of [36(NSI)]. 86 8.2.2.2. Preparation of 58a[NSI] 87 8.2.2.3. Preparation of 58b[N(SO2Ph)2] 88 8.2.3. Preparation of fluorophosphonium triflate salts 88 8.2.3.1. Preparation of 36[OTf] 89 8.2.3.2. Preparation of 36[H(OTf)2] 89 8.2.3.3. Preparation of 58a[OTf] 90 8.2.3.4. Preparation of 58b[OTf] 91 8.2.3.5. Preparation of 58c[OTf] 91 8.2.3.6. Preparation of 59a[OTf] 92 8.2.3.7. Preparation of 59b[OTf] 93 8.2.3.8. Preparation of 60Mea[OTf]2 94 8.2.3.9. Preparation of 60iPra[OTf]2 94 8.2.2.10. Preparation of 60Meb[OTf]2 95 8.2.3.11. Preparation of 60iPrb[OTf]2 96 8.2.3.12. Preparation of 61Me[OTf]3 97 8.2.3.13. Preparation of 61iPr[OTf]3 97 8.2.4. Reaction of fluorophosphonium triflate salts with nucleophiles 98 8.2.4.1. Preparation of 62a[OTf] 98 8.2.4.2. Preparation of 62b[OTf] 99 8.2.4.3. Preparation of 62c[OTf] 100 8.2.4.4. Preparation of 63 100 8.2.4.5. Preparation of 65 101 8.2.4.6. Preparation of 69a[OTf] 102 8.2.4.7. Preparation of 69b[OTf] 103 8.2.5. Synthesis of H[N(SO2R)(SO2Ph)] and corresponding sodium salt 103 8.2.5.1. General procedure for the formation of N-sulfonyl-sulfonamides 103 8.2.5.2. General procedure for the formation of sodium bis(sulfonyl)amides 104 8.2.5.3. Preparation of HN(SO2Ph)2, Na[N(SO2Ph)2] and [nBu4N][N(SO2Ph)2] 104 8.2.5.4. Preparation of 81a and 82a 105 8.2.5.5. Preparation of 81b and 82b 106 8.2.5.6. Preparation of 81c and 82c 106 8.2.5.7. Preparation of 81d and 82d 107 8.2.5.8. Preparation of 81e and 82e 108 8.2.5.9. Preparation of 81f and 82f 108 8.2.5.10. Preparation of 81g and 82g 109 8.2.5.11. Preparation of 81h and 82h 109 8.2.6. Synthesis of N-sulfonyl amidines 110 8.2.6.1. General procedure for the catalytic formation of N-sulfonyl amidines 110 8.2.6.2. Preparation of 64 110 8.2.6.3. Preparation of 72 111 8.2.6.4. Preparation of 73 112 8.2.6.5. Preparation of 74 112 8.2.6.6. Preparation of 75 113 8.2.6.7. Preparation of 76 114 8.2.6.8. Preparation of 77 114 8.2.6.9. Preparation of 78 115 8.2.6.10. Preparation of 79 116 8.2.6.11. Preparation of 80a,b 116 8.2.6.12. Preparation of 83b 117 8.2.6.13. Preparation of 83c 118 8.2.6.14. Preparation of 83d 119 8.2.6.15. Preparation of 83e 119 8.2.6.16. Preparation of 83f 120 8.2.6.17. Preparation of 83g 121 8.2.6.18. Preparation of 83h 122 8.3. Experimental details for CHAPTER II 123 8.3.1. Preparation of N-containing phosphanes 123 8.3.1.1. Preparation of 2-(bis(perfluorophenyl)phosphaneyl)pyridine 123 8.3.1.2. Preparation of 2-(bis(perfluorophenyl)phosphaneyl)-1-methylimidazole 124 8.3.1.3. Preparation of 2-(bis(perfluorophenyl)phosphaneyl)-N,N-dimethylaniline 124 8.3.2. Preparation of N/P Frustrated Lewis Pairs 125 8.3.2.1. General procedure for the synthesis of N/P-Frustrated Lewis pairs 125 8.3.2.2. Preparation of 85[OTf] 126 8.3.2.3. Preparation of 86[OTf] 126 8.3.2.4. Preparation of 87[OTf] 127 8.3.2.5. Preparation of 88[OTf] 128 8.3.2.6. Preparation of 89[OTf] 129 8.3.3. Synthesis of compound 84[OTf] 130 8.3.4. Reaction of N/P FLP with carbonyls, nitriles or acetylenes 131 8.3.4.1. General reaction conditions for the reaction of N/P FLP with carbonyls and nitriles 131 8.3.4.2. Preparation of 90[OTf] 131 8.3.4.3. Preparation of 91[OTf] 132 8.3.4.4. Preparation of 92[OTf] 133 8.3.4.5. Preparation of 93a[OTf] 134 8.3.4.6. Preparation of 93b[OTf] 134 8.3.4.7. Preparation of 94[OTf] 135 8.3.4.8. Preparation of 95[OTf] 136 8.3.4.9. Preparation of 96[OTf] 137 8.3.4.10. Preparation of 97a[OTf] 138 8.3.4.11. Preparation of 97b[OTf] 139 8.3.4.12. Preparation of 99a[OTf]2 140 8.3.4.13 Preparation of 100b[OTf] 141 8.3.5. Reaction of N/P FLPs with CO2 142 8.3.5.1 Reaction of 85[OTf] with CO2 142 8.3.5.2 Reaction of 86[OTf] with CO2 142 8.4. Experimental details for CHAPTER III 144 8.4.1 Synthesis of 105a,b[OTf] and 106c 144 8.4.1.1. General procedure for the reaction of fluorophosphonium triflate with Me3SiCN 144 8.4.1.2. Preparation of 105a[OTf] 144 8.4.1.3. Preparation of 105b[OTf] 145 8.4.1.4. Preparation of 106c 145 8.4.2. Reaction of fluorophosphonium triflate salt with Me3SiN3 146 8.4.2.1. General procedure for preparation of azidofluorophosphorane 146 8.4.2.2. General procedure for preparation of azidofluorophosphonium triflate salts 146 8.4.2.3. Preparation of 107a[OTf] 146 8.4.2.4. Preparation of 107b[OTf] 147 8.4.2.5. Preparation of 107c[OTf] 147 8.4.2.6. Preparation of 108c 148 8.4.2.7. Preparation of 109[OTf] 149 8.4.2.8. Preparation of 110[OTf]2 149 8.4.2.9. Preparation of 113[OTf]3 150 8.4.2.10. Preparation of 114[OTf] 151 8.4.2.11. Preparation of 115[OTf] 151 8.4.2.12. Preparation of 116[OTf] 152 8.4.3 Transformation of azido-fluorophosphorane under heating conditions 153 8.4.3.1 Preparation of 118 153 8.4.3.2 Preparation of 120a,b[OTf] 154 9. Crystallographic details 156 9.1. X-ray Diffraction refinements 156 9.2. Crystallographic details for CHAPTER I 157 9.3. Crystallographic details for CHAPTER II 169 9.4. Crystallographic details for CHAPTER III 176 10. Computational methods 179 11. Abbreviations 181 12. Nomenclature of compounds according to IUPAC recommendations 183 13. References 187 14. Acknowledgment 205 15. Publications and conference contributions 207 15.1. Peer-reviewed publication 207 15.2. Poster presentations 207 Versicherung 209 Erklärung 209

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