Synthesis,Crystal Structures And Properties Of Metal-oxo/-halo Clusters

Metal cluster-based hybrid crystal materials are a kind of materials possessing excellent physical and chemical properties,due to the performance advantages of inorganic components and the structure characteristics of the organic material and arouse people's attention.With metal cluster as the secondary building units,its inorganic components could serve as high-connected nodes,making the metal cluster-based hybrid materials show unique topology structure;On the other hand,Low dimensional metal clusters compound can show the special properties in the field of optics,electricity,magnetism,catalysis,separation and adsorption,and so on,resulting in important research value and application prospect.Embarking from the design of new cluster structure,different series of clusters-based with different structure types crystal materials have been prepared by hydro/solvothermal method and solvent volatilization method.And their structures were studied by UV-vis,FT-IR,thermogravimetric analysis?TGA?,elemental analysis and single crystal X-ray diffraction?SXRD?and powder X-ray diffraction?PXRD?.And the optical properties,thermal stability and fluorescence properties were also tested.The main research results are as follows:?1?Two isostructural rare earth-cadmium hydroxycarbonates crystal materials,namely,RE₂Cd?CO₃??OH?₆?RE=Y?1?,Er?2??,have been synthesized by the method of hydrothermal with using Cd?NO₃?₂.4H₂O as cadmium source.The structure analysis indicated that they show 3D complicated network based on[REO₈]and[Cd O₆]polyhedra,which are connected by[CO₃]triangle unit via corner-sharing or edge-sharing.Moreover,Performance analysis shows that they have strong blue fluorescence emission properties.?2?Two novel cadmium germanium phosphate crystal materials,namely,[Cd Ge??₂-O??HPO₄?₂?H₂O?₂].H₂O?3?and Cd₇Ge?PO₄?₆?4?,have been prepared with using Cd?NO₃?₂.4H₂O as cadmium source by the method of hydro/solvothermal,respectively.The structure analysis indicates that the compound 3 features a 2D layer structure consisting of[Ge O₆]octahedron and[Cd O₆]octahedron,water molecules filled between layer and layer;Compound 4 shows[Cd O₆]octahedron-based 3D dense structure,[Ge O₆]and[PO₄]polyhedron filled a six-member ring formed[Cd O₆]octahedron through coordination key.Moreover,performance analysis shows that they have strong blue fluorescence emission properties;Compound 4 is thermally stable up to about 800?.There is no phase-change from room-temperature to 800?,which Suggests that this is a very good thermal stability of materials.?3?Solvothermal reactions of Hg I₂,4,4'-vinylenedipyridine and HI in alcoholic solution?methanol,ethanol or pentanol?gave rise to a family of organic-inorganic hybrid complexes,formulated as[C₁₄H₁₆N₂][I₄]^2-?5?,[C₁₆H₂₀N₂][Hg I₄]?6?and[C₂₂H₃₂N₂]₄[Hg I₄]₄?7?.In this reaction,4,4'-vinylenedipyridine acts as organic ligands,mercury iodide as inorganic components,different kinds of alcohols as alkylation reagents.The structural analysis shows that they are all discrete polyiodide or mercury?II?iodide compounds,the C–H…I hydrogen bonds between organic cation and[I₄]^2-in compound 5 lead to the one dimensional supramolecular structure;while compounds 6 and 7 have the similar zero-dimensional discrete structure.