Hydrothermal synthesis and characterization of nickel-manganese based extended materials and aspects of crystal growth in selected metal complexes of 2,2'-bipyridine N,N' dioxide

Part A. The new neutral 2D layered structure, [Ni(OH) 2][Ni1.15Mn0.51 Cl0.36F1.56(OH)1.26] has been obtained using hydrothermal methods and the structure has been determined by powder X-ray diffraction. The title compound crystallizes in the R-3 m space group with a = 3.10028(10) A; c = 37.3467 A; alpha = 90.0° gamma = 120.0; V = 310.87436(A)3 and Z = 3. The refinement led to R1 = 0.0542 and wR2 = 0.0713 (all data). Elemental and thermal analyses closely confirm the values deduced from the X-ray structure determination. Preliminary magnetic susceptibility measurements point to possibility of spin glass phase transition.; Hybrid inorganic-organic 2D Nickel succinate material has been hydrothermally synthesized. The X-ray structure has been determined. Distinct Ni atoms in different coordination environments are isolated from each other via succinate moieties. Thermogravimmetric analysis reveals the material's rare high thermal stability of up to 380°C, which compares well to a 3D open framework nickel succinate system in a prior study.; Part B. The growing interest in developing efficient light conversion molecular devices (LCMDs) necessitates the need for new fluorescent materials. Ideal physicochemical properties of the materials include ligand absorption, efficient metal to ligand transfer, and strong luminescence with a relatively long decay time. The design of such material requires distinct absorbing (ligand) and emitting (metal ion) components. While Eu3+ cation has a non-degenerate emitting level, 2,2'-bipyridine N,N dioxide is a heterocyclic ligand known to exhibit strong luminescence. We report the crystal structure of a new europium based material, [EuCl3(C 10H8N2O2)˙2CH3OH]. Other measurements are also described, including IR and UV-Vis spectroscopies, and elemental analysis. Eu3+ complexes can potentially be utilized as local probes in biochemical systems.; Single crystal X-ray analysis in chapter three reveal that the title compound, Cu(C10H8N2O2)2 (ClO4)2(H2O) is formed by discrete molecules in which the Cu atom is five coordinated. The title complex Cu 2(C10H8N2O2)2Br 4 is also a molecular compound, but with two crystallographically independent complexes. Both complexes display a distorted square pyramidal environment about the copper centres.; The crystal structures of some of the mercury halide complexes of 2,2'-bipyridine N,N' dioxide ligand, have been determined. The title compound [HgI2(C 10H8N2O2)], is found to be an example of a mercury halide complex of the chelating bipyO2 ligand. As observed for similar compounds, the coordination polyhedron of the Hg atom is a severely distorted tetrahedron, in which two I atoms and two O atoms of the ligand coordinate Hg. The mercury complex [HgBr2(C 10H8N2O2)], has an Hg atom surrounded by two Br atoms and two O atoms from a chelating bipyO2 ligand (bipyO2 is 2,2'-bipyridine N,N'-dioxide), forming a severely distorted tetrahedron. In addition, two weak Hg--Br bonds link these complexes into a chain. In the crystal structure of the title compound, [HgCl2(C 10H8N2O2)], the Hg atom has severely distorted tetrahedral coordination by two Cl atoms and by two O atoms of the chelating ligand. Additional weak Hg--Cl bonds link the molecules into a chain.; X-ray characterization of Pb(C10H8N2O 2)(NO3)2 shows its crystallization in a coordination environment best described as distorted trigonal prismatic. Chelation of both the bidentate ligand and nitrate ion is evident. Extensive hydrogen bonding network leads to zigzag stacks of cations along the b axis. The PbII ion is six-coordinated by the two oxygen atoms, of the ligand, four oxygen atoms of two chelating nitrate ions in a distorted geometry.; In all of the above cases of metal complexes, unit cell parameters have been successfully determined using suitably grown crystals by the technique of slow evaporation and then studied by single crystal X-ray diffraction technique.