The work is focused on the investigation of synthesis and structure of crystalline coordination networks by combining first a row transition metal ion with one anionic and one neutral bridging ligand. In the field of crystalline coordination networks, the goal is to synthesize porous 3D crystalline coordination networks with molecular sized cavities. The materials are characterized by XRD and TGA. It is important to understand the structural topologies to develop practical applications, such as gas storage, gas separation, and catalysis. The bi- and tetra-dentate flexible imidazole ligands, 9,10-bis(imidazol-1-ylmethyl)anthracene (Chapter 2) and 1, 2, 4, 5-tetrakis(imidazol-1ylmethyl)benzene (Chapter 3), are synthesized and used as linkers to construct 1D, 2D, and 3D crystalline coordination networks with cobalt(II) or zinc(II) cations and H3BTC anions under solvothermal conditions. Two 1D chain networks, [M(HBTC²⁻)(C₂₂H₁₈N₄)(H₂O)₂]•H₂O, are constructed from M(Zn(II) or Co(II)), H₃BTC, and 9,10-bis(imidazol-1-ylmethyl)anthracene (Compound 2.1 and 2.2). These two 1D zigzag chains are linked into infinite 2D sheets by inter-chain π•••π stacking and hydrogen bonding. ⁺ Two 2D and one 3D cobalt(II) coordination networks are constructed from the tetradentate imidazole ligand and H3BTC. Compound 3.1 has a 2D corrugated sheet structure that is linked by inter-layer π•••π stacking and hydrogen bonding. Compound 3.2 has a 2D sheet structure. These sheets are interconnected by hydrogen bonds at the free acid group of the HBTC²⁻ ligand. Compound 3.3 forms a two fold interpenetrated 3D network structure. Void spaces in the structure are filled with six water molecules. Six 3D cobalt (II) coordination networks are constructed with bidentate rigid imidazole containing neutral ligands, 1,4-bis(imidazol-1-yl)benzene(L1), 1,4-bis(imidazol-1-yl)naphthalene(L2), and 9,10-bis(imidazol-1-yl)anthracene(L3), and H₂BDC or H₃BTC anion (Chapter 4). In 4.1-4.3, L1-L3 affects on degree of interpenetrations constructed with H₂BDC ligand. In 4.1 and 4.2 are interpenetrating 3D networks with no accessible void space. In 4.3, void spaces of 3D networks are filled with 2D sheets. Compounds 4.4-4.6 are prepared by different concentrations of starting materials and different solvents. In 4.4-4.6, L3 serves as a pillar building block to construct 3D networks by applying with H₃BTC ligand. The solvent exchange experiment for 4.4 is further discussed. / Ph. D.

Investigations in the 99mTc chemistry are stimulated by the search for new radiopharmaceuticals for nuclear medical applications. To understand the coordination mode of Tc with various complexing agents, macroscopic studies of technetium coordination chemistry are often performed using the low energy ß-emitting radionuclide 99Tc, which has a much longer half life (t1/2 = 2.12 x 105 years) than 99mTc, in the mg level. Investigations of Re coordination chemistry are done in conjunction with Tc studies because Re possesses chemical properties similar to those of Tc. For some chemical tasks, Re provides a non-radioactive alternative to work with Tc radioisotopes. In addition, 186Re and 188Re are of great interest to nuclear medicine as they possess nuclear properties favorable for use in therapeutic radiopharmaceuticals. Our investigations of Tc and Re coordination chemistry are toward this goal. A large series of technetium and rhenium complexes resulted from this studies have been characterized by X-ray crystal structure determinations. This survey covers the structural investigations performed by P.Leibnitz and G.Reck (BAM) from 1992 till now. It summarizes results obtained in the Rossendorf technetium group and is not intended to compete with the well-written reviews published so far.

Investigations in the 99mTc chemistry are stimulated by the search for new radiopharmaceuticals for nuclear medical applications. To understand the coordination mode of Tc with various complexing agents, macroscopic studies of technetium coordination chemistry are often performed using the low energy ß-emitting radionuclide 99Tc, which has a much longer half life (t1/2 = 2.12 x 105 years) than 99mTc, in the mg level. Investigations of Re coordination chemistry are done in conjunction with Tc studies because Re possesses chemical properties similar to those of Tc. For some chemical tasks, Re provides a non-radioactive alternative to work with Tc radioisotopes. In addition, 186Re and 188Re are of great interest to nuclear medicine as they possess nuclear properties favorable for use in therapeutic radiopharmaceuticals. Our investigations of Tc and Re coordination chemistry are toward this goal. A large series of technetium and rhenium complexes resulted from this studies have been characterized by X-ray crystal structure determinations. This survey covers the structural investigations performed by P.Leibnitz and G.Reck (BAM) from 1992 till now. It summarizes results obtained in the Rossendorf technetium group and is not intended to compete with the well-written reviews published so far.

In this thesis complexes of acylchalcogoureas with cadmium (II), lead (II) and nickel (II) have been synthesised and investigated as single source precursors for the formation of metal chalcogenide thin films viaaerosol assisted chemical vapour deposition (AACVD). Routes to binary thin films have been explored using homoleptic complexes of the general structure bis(N,N-diethyl-N'-naphthoylchalcogoureato)metal(II). Analysis of the thin films produced showed the successful deposition of the binary materials from the synthesised complexes when characterised by powder XRD, ICP-OES, SEM and EDX. Routes to ternary thin films with the general structure MExE'1-x, where M represents a metal (Cd, Ni and Pb); and E chalcogen (S or Se) have been investigated using heteroleptic metal complexes of cadmium, nickel or lead including different chalcogen containing N,N-diethyl-N'-naphthoylchalcogoureato ligands and diethyldithiocarbamate. The precursors were fully characterised and novel compounds had their crystal structures determined. The heteroleptic complexes were thermolysed by AACVD forming the MExE'1-x thin films. In the cases of lead, nickel and cadmium the thin films produced showed that the composition of the film tended heavily towards the metal selenide. Ternary films of type MS1-xSex was prepared by mixing their binary precursors of type bis(N,N-diethyl-N'-naphthoylselenoureato)metal(II) and bis(N,N-diethyl-N'-naphthoylthioureato)metal(II) [metal = Cd, Ni and Pb]. In the case of lead and cadmium chalcogenide films variation of the ratio of sulphur and selenium containing precursors allowed for the full transition in composition between metal sulphide and metal selenide. In the case of CdS1-xSexthe band gap of the films was determined from UV-visible spectroscopy to vary from 2.4 eV (CdS) to 1.7 eV(CdSe). In the case of NiS1-xSex the movement from sulphide to selenide was less simple with multiple phases of nickel chalcogenides produced.

The correlation between NMR chemical shifts of interstitial atoms and electronic structures of boron- and carbon-centered hexazirconium halide clusters was investigated by density functional theory (DFT) calculation. The influences of bridging halide and terminal ligand variations on electronic structure were examined respectively. Inverse proportionality was found between the chemical shifts and the calculated energy gaps between two Kohn-Sham orbitals of t1u symmetry, which arose from the bonding and antibonding interaction between the zirconium cage bonding orbitals and the interstitial 2p orbitals. Chemical shielding properties of the interstitial atoms were calculated with Gauge Including Atomic Orbital (GIAO) method. Stepwise ligand substitution of terminal chlorides on [(Zr6CCl12)Cl6]4-cluster by tri(n-butyl)-phosphine oxide (Bu3PO) was conducted with the aid of TlPF6. Composition of the reaction mixtures was analyzed by use of both 13C and 31P NMR. A preliminary scheme for synthesis and separation of [(Zr6CCl12)Cl6-x(Bu3PO)x]x-4 (x = 3 ?? 5) mixture based on solubility difference was reevaluated. Three 1,10-phenanthroline based bidentate ligands, namely, 2,9-Bis(diphenyl-phosphinyl)-1,10-phenanthroline, 2,9-Bis(diethoxyphosphoryl)-1,10-phenanthroline, and 2,9-Bis(di-n-butoxyphosphoryl)-1,10-phenantholine, were synthesized for bridge-chelating the hexazirconium clusters. Coordination chemistry of these ligands with the [Zr6BCl12] and [Zr6CCl12] clusters was subject to preliminary investigation.

The correlation between NMR chemical shifts of interstitial atoms and electronic structures of boron- and carbon-centered hexazirconium halide clusters was investigated by density functional theory (DFT) calculation. The influences of bridging halide and terminal ligand variations on electronic structure were examined respectively. Inverse proportionality was found between the chemical shifts and the calculated energy gaps between two Kohn-Sham orbitals of t1u symmetry, which arose from the bonding and antibonding interaction between the zirconium cage bonding orbitals and the interstitial 2p orbitals. Chemical shielding properties of the interstitial atoms were calculated with Gauge Including Atomic Orbital (GIAO) method. Stepwise ligand substitution of terminal chlorides on [(Zr6CCl12)Cl6]4-cluster by tri(n-butyl)-phosphine oxide (Bu3PO) was conducted with the aid of TlPF6. Composition of the reaction mixtures was analyzed by use of both 13C and 31P NMR. A preliminary scheme for synthesis and separation of [(Zr6CCl12)Cl6-x(Bu3PO)x]x-4 (x = 3 ?? 5) mixture based on solubility difference was reevaluated. Three 1,10-phenanthroline based bidentate ligands, namely, 2,9-Bis(diphenyl-phosphinyl)-1,10-phenanthroline, 2,9-Bis(diethoxyphosphoryl)-1,10-phenanthroline, and 2,9-Bis(di-n-butoxyphosphoryl)-1,10-phenantholine, were synthesized for bridge-chelating the hexazirconium clusters. Coordination chemistry of these ligands with the [Zr6BCl12] and [Zr6CCl12] clusters was subject to preliminary investigation.

Les analogues de nucléosides sont d'une importance considérable dans la recherche de nouveaux candidats médicaments antiviraux et anticancéreux. La ribavirine est en effet le premier nucléoside triazole antiviral synthétique. Elle est toujours activement utilisée en milieu hospitalier pour le traitement de l'hépatite C et celui des pandémies virales émergentes. Récemment, le besoin de nouveaux agents thérapeutiques efficaces dotés de nouveaux mécanismes d'action a donc créé un regain d'intérêt dans la création de nouvelles entités structurelles de nucléosides triazoles. Au cours de mon doctorat, j’ai été activement engagée dans l’élaboration de nouvelles structures O-arylées et S-arylées de nucléosides triazoles. Les nucléosides triazoles O-arylés ont été obtenus par substitution nucléophile aromatique initiée par micro-ondes, tandis que les nucléosides triazoles S-arylés ont été synthétisés par réaction de couplage C-S en utilisant un catalyseur palladié possédant des ligands mixtes nouvellement mis au point dans notre laboratoire. Le concept du système de catalyseur à ligands mixtes est extrêmement avantageux et enrichissant puisqu’il permet de combiner de façon rationnelle des ligands possédant des fonctionnalités complémentaires afin de promouvoir des réactions avec des substrats pour lesquels ces réactions sont très compliquées. Enfin, afin d'améliorer la solubilité dans l'eau des analogues nucléosidiques triazoles actifs que nous avons identifiés, j’ai tenté de conjuguer le nucléoside triazole à un dendrimère amphiphile dans le but d'élaborer un système de délivrance efficace des médicaments et ainsi d’améliorer leur biodisponibilité. / Nucleoside mimics are of considerable importance in the search of antiviral and anticancer drug candidates. One noteworthy example is ribavirin, the first synthetic antiviral triazole nucleoside discovered 40 years ago, which is still actively in clinic use for treating hepatitis C infection and emerging viral pandemics. Recently, ribavirin has been also reported to demonstrate apoptosis-related anticancer effects and is in clinical trial for treating leukemia. Consequently, there is a renewed interest in creating new structural entities of triazole nucleosides with the aim of developing potent therapeutic agents with novel mechanisms of action. During my PhD program, I have been actively engaged in constructing structurally novel O-arylated and S-arylated triazole nucleosides. The O-arylated triazole nucleosides were obtained via microwave promoted aromatic nucleophilic substitution, whereas the S-arylated triazole nucleosides were synthesized via C-S coupling reaction using our newly developed mixed ligand Pd catalyst (Pd2(dba)3/Xantphos/CyPF-tBu). The concept of the mixed ligand catalyst system is extremely advantageous and rewarding, offering a unique opportunity to rationally combine ligands with complementary features in order to promote the reactions with challenging substrates which are otherwise difficult to proceed. Finally, in order to improve bioavailability of the active triazole nucleoside analogues identified in our group, I have attempted to conjugate the triazole nucleoside to an amphiphilic dendrimer in the view to establishing an effective drug delivery system and offering a better bioavailability.