The Synthesis And Luminescent Properties Of D¹⁰ Metal-Organic Coordination Polymers

As novel inorganic-organic hybrid materials, d10 metal-organic coordination polymers not only have excellent properties and wide application in luminescence,electrics, magnetism, catalysis, and gas storage due to their various structures and compositions, but also play important roles in bioinorganic chemistry, life science, etc due to some of them possess various physiological functions. In this thesis, the best reaction conditions of two two kinds of d10 metal-organic coordination polymers constructed by covalent molecules were explored, and luminescent properties of targeted coordination ploymers were also analysized by the combination of experiments and theoretical calculations.Through controlling the ratios of metal to ligand, solvent polarities, reaction temperatures, etc, four d10metal-organic coordination polymers, [Cu(CN)(bipy)]n(1),Cu3(CN)3(4,4’,-Hbpt)2(2), [Zn(4,4′-Hbpt)Cl2]n(3), [Zn(4,4′-Hbpt)Br2]n(4) were synthesized by hydrothermal/solvothermal syntheses. X-ray single crystal diffractions exhibit that complex 1 has a 1D helical structure, which further forms a complex 3D structure via weak π-π interations, complex 2 displays a five-fold interpenetrated structurs with dmd topology, complex 3 is a 1D helical structure, while complex 4displays a 1D zig-zag chain structure. The four complexes were also characterized by FT-IR, elemental analysis, XRD, and photoluminescence. Furthermore, the isostructure of complexes 3 and 4, Zn(4,4’-Hbpt)Br2]n(5) and [Zn(4,4’-Hbpt)Cl2]n(6) were simulated by Material Studio program(MS), respectively.The molecular orbitals of excited-state and their electron-density distribution of the corresponding frontier molecular orbitals of complex 1 were calculated by timedependent Density Functional theory with Gaussian program. The bond structures and state density of the d10 metal polymer was also calculated by DFT theory with Material studio program(CASTEP module). The origins of luminescence of all coordination polymers were explored by analyzing their electron-density distribution of the corresponding frontier molecular orbitals or their bond structures. The luminescent mechanism of these d10 metal-organic coordination polymers were explord by the combination of photoluminescence experiments and the crystal structures, which cansupply theoretical guidance for the preparation of luminescent materials with practical application values. The results display that the luminescences of complex 1 and 2 are mainly orginated from the combination of metal to ligand charge transfer(MLCT) and ligand to ligand charge transfer(LLCT), while the luminescences of complex 3- 6 are mostly orginated from the combination of ligand to metal charge transfer(MLCT) and ligand to ligand charge transfer(LLCT).