Mo(W)/S/Cu(Ag) Clusters And N-heterocycle Based Coordination Polymer:Syntheses,Structures And Optical Properties

The dissertation mainly discusses the synthesis and crystal structures of W(Mo)/S/Cu(Ag) heterothiometallic clusters and N-heterocycle based Coordination polymer. Two novel3D W(Mo)/S/Cu clusters and two new3D coordination polymers have been prepared by one-step solvothermal synthesis method. And three1D W/S/Ag clusters have been synthesized in the liquid diffusion method at room temperature. The luminescent properties of three synthetic polymers were investigated.They are as follows:(1)[WS4Cu4(CN)2(4-bpt)]n (4-bpt=4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole)(2)[MoS4Cu4(CN)2(4-bpt)·CH3CN]n(3){[W3S12Ag3][Sm(DMF)(DMSO)7]}n(4){[W3S12Ag3][Er(DMF)(DMSO)7]}n(5){[W3S12Ag3][Dy(DMF)4(DMSO)4]}n(6)[Cu2SCN(4-bpt)]n(7)[Zn(C7H5N2)2·H2O]n (C7H5N2=benzimidazolyl-)1. The influence on structure of polymeric clusters by the complicated coordination mode of multifunctional ligand has been studied. In employment of one-step solvothermal synthesis method, two micropore3D Mo(W)/S/Cu clusters bearing more one plane than fly-wheel cluster unit [MS4Cu3]+(M=W, Mo) have been prepared, in which the ligand4-bpt can be served as a trident connector linked to the cluster units [MS4Cu4]2+(M=W, Mo), and their voidages calculated by Platon are53.5%、48.1%, and were characterized by FT-IR, elemental analysis, single-crystal X-ray diffracrion, flurescence emission and UV-vis spectra.2. The effect on structure of polymeric clusters by the anion in silver compound has been researched. The precursor Ag(dmpymt)(Hdmpymt=4,6-dimethylpyrimidine-2-thiol) as Ag+source and different solvent-coordinated balance cations as templates have been applied to direct three W/S/Ag clusters, The obtained clusters, i.e.1:2ladder chain-cluster3and4, and the linear chain-cluster5, have been well-characterized by the FT-IR, UV-vis spectra, elemental analysis and single-crystal X-ray diffracrion.3. In employment of one-step solvothermal synthesis method, ligands (benzimidazole,4-bpt) in v-shaped coordination modes reacted with transition metal compound resulting in the formation of two3D coordination polymer. By the change of the spatial configuration of the ligand in the self-assembly process, the polymers with novel structures have been synthetized, and were characterized by the FT-IR, UV-vis spectra, elemental analysis, and single-crystal X-ray diffraction. And the luminescent property of polymer6has been studied.