The Syntheses,Structures And Properties Of Chalcogenidometalates Of Sn,Sb And Hg Containing Metal Complex Cations

Chalcogenidometalates of groups 12,14 and 15 elements have important application prospects in many fields,such as photoconductor,catalysis,semiconductor materials and nolinear optics,due to their excellent photoelectric,electrochemical properties and structural diversity.In recent years,hydrothermal synthesis has been widely used in the preparation of chalcogenidometalates,because of the advantages of simple operation,high controllability and high purity of products.In this thesis,introducing transition metals?TM?or lanthanide metals?Ln?into the synthetic system M/Q?M=Sn,Sb,Hg;Q=Se,Te?,under solvothemermal conditions,a series of chalcogenidometalates of Sn,Sb and Hg containing transition metals complex cations or lanthanide complex cations were successfully synthesized and characterized.The effects of the kinds of ligands and solvents and reaction temperatures on the synthesis of compounds were studied.Furthermore,the luminescence and photocatalytic properties of some compounds were investigated.In this thesis,the major contents were summarized as following.1.The reaction of TM/Sn/Se system in different solvents were studied by using en,dien,andtirenasligands.TheFe-containingselenidostannates[H2en][H2dien][Fe?dien?2]2?Sn2Se6?2?1?,[H2en][Fe?dien?2]?Sn2Se6?·0.5en?2?,[Fe?en??trien?]2Sn2Se6?3?and[Fe?en?3]Sn3Se8?4?were synthesized under solvothermal conditions.The subtle influence of solvent on the solvethermal syntheses of crystalline selenidostannates was discussed.2.Theselenidoantimonatescontaininglanthanidecomplexcations{[Ln?tepa??Cl?][Ln?tepa??OH?]2?SbSe4?2}n?Ln=Sm?5?,Eu?6??and[H2tepa]{[Ln?tepa??SbSe4?]2?OH?2}?Ln=Eu?7?,Ho?8?,Tm?9??were synthesized with tepa as solvent.Compounds 5 and 6 contain?-1?:2?-SbSe₄,and 7 and 8 contain mono-SbSe₄ ligands.The effects of the structure of ethylene polyamine and the size of Ln?III?ion on the coordination type of tetrahedral[SbSe4]^3-ion was discussed.It is notable that the bidenate1?:2?-SbSe4 bridging ligand in 5 and 6 is firstly observed in the systematic syntheses of the Ln/Sb/Se system.3.Using trien and tepa as ligands,and elemental Te as precursor in low temperature range,with assistance of hydrazine of high reactivity,transition metal-containing telluromercurates[Mn?trien??N2H4?2]2[Hg2Te4]2?10?,[Mn?trien??N2H4?2]Hg2Te4?11?,[Mn?tepa??N2H4?]2Hg4Te12?12?,[TM?trien?][Hg2Te4]?TM=Mn?13?,Zn?14??and[Zn?atep?]2Hg5Te12?15?were prepared in one step at a lower temperature range.The influence of polyamino denticities on the coordination chemidtry of the telluromercurate anions was investigated.Compounds 13 and 14,with the HgTe binary anions coordinating to the centers of TM?II?complex cations,were obtained for the first time in the TM/Hg/Te system.The photocatalytic activity of compounds 10,12 and 13 was investigated through the experiments of degradation of organic dyes.4.The structures of the synthesized compounds were determined by single crystal X-ray diffractometer.The purity of the samples were measured by XRD.The composition of the compounds were characterized by XRD,elemental analysis and IR spectra.The optical properties and thermal stability of the compounds and the fluorescence properties of the lanthanide compounds were determined.