Syntheses And Properties Of D¹⁰ Metal Coordination Polymer With S/n-containing Ligand

The d¹⁰ metal coordination polymer with S/N-containing heterocyclic ligand due to good properties such as optical physics, photochemical function, have become one of advancing field of current chemical and material science. The synthesis and design of new S/N heterocyclic ligands and the study of their CuI, HgII complexes structure and property are done the following:a) Two new single thioether ligands [2-methyl-5-(1-n-hexadecysulfanyl) -1,3,4- Thiadiazole (L¹) and 2- (1-n-hexadecysulfanyl) pyridine (L²)] have been designed and synthesized and their new CuI complexes 1, 2 have been prepared. The structure of ligands and complexes was characterized by IR,1H-NMR and elemental analysis.b) Dithioether ligand 3,6-bis(2-pyridylsulfhydryl)pyridazine(L3) has been designed and synthesized and their HgI2, HgBr2 and CuI novel complexes( 3, 4 and 5) have been prepared. Their structures were characterized by IR,1H-NMR and elemental analysis.c) The crystal structures of five complexes are characterized by single crystal X-ray diffraction techniques, and they are all coordination polymer. Complexs 1, 2 is one-dimensional ladder chain coordination polymer. Complexs 3, 4 is "Z" shaped one-dimensional chain coordination polymer. Complex 5 is one-dimensional tree branched like coordination polymer. Cu-I bond connect (CuI)n chain to form double-strand ladder structure in complexes 1, 2. Complexes 1, 2, 5 are CuI coordination polymer, and the ligands have different coordination model. Complexes 3, 4 and 5 are the different complexes of L3 ligand, different structure of coordination polymers are obtained due to the different metal ions.d) The electrochemical properties of coordination polymer are determined by cyclic voltammetry. Complexes 1, 2 and 5 are quasi-reversible electrode reaction and complexes 3,4 are irreversible electrode reaction.e) The semiconductor property of the coordination polymer are determined by UV-VIS diffuse reflectance. Energy gap of complexes 1, 2, 3, 4, 5 are 2.9 eV, 2.8 eV, 3.3 eV, 3.4 eV, 1.8eV, respectively. All the complexes have semiconductor property.f) The thermal stability of coordination polymer 1, 2 are determined. Complexes 1, 2 have been two phases of the thermal decomposition process of weight loss, and they have good stability.