含氰金属配体桥连的钼(钨)铜硫簇基配位聚合物的组装，结构及非线性光学研究

Assembly of Mo(W)/Cu/S cluster-based coordination polymers remains one of the hottest topics in the current functional coordination polymers. These clusters exhibit potential applications in advanced functional materials such as third-order nonlinear optical (NLO) materials. This project aims at rational assembly of metal cyano-bridged Mo(W)/Cu/S cluster-based coordination polymers from reactions of [Tp*MS3]- (M = Mo,W; Tp* = hydridotris(3,5-dialkylpyrazol-1-yl)borate) or Mo(W)/Cu/S cluster precursor clusters like [Tp*MS3(CuX)n]- (n = 2~3; X = Cl, Br, I) (that possess easily-leaving terminal groups and some NLO responses) with various metal cyanides such as MCN、K[M(CN)2] (M = Cu(I), Ag(I), Au(I)), [Fe(CN)6]2-/3-, [M(CN)4]2- (M = Pt, Pd, Ni). After determining the crystal structures of these compounds, we could explore synthetic methodologies of these metal cyano-bridged Mo(W)/Cu/S cluster-based coordination polymers. Through determining their third-order NLO properties in solution, we could investigate the possible relation between the structure and NLO property. It is anticipated that when this project is finished, we could expand our understanding about the synthetic and structural chemsitry of the mixed-metal sulfide clusters, and also the scope of the third-order NLO materials, and lay a good foundation for the development of third-order NLO materials with better NLO performances.

钼(钨)铜硫簇基配位聚合物的合成是当今功能配位聚合物领域最热门的研究课题之一，这类簇合物在先进材料如非线性光学材料等呈现出潜在的应用前景。本课题试图用[Tp*MS3]-或具有易取代端基基团和三阶非线性响应的Mo(W)/Cu/S前驱簇如[Tp*MS3(CuX)n]-与不同的金属氰化物如MCN、K[M(CN)2] (M = Cu(I), Ag(I), Au(I))等反应，制备金属氰桥连接的簇基配位聚合物，通过单晶X-射线衍射方法解析它们的晶体结构，探索此类金属氰桥连接的簇基配位聚合物合成反应的规律；测定这些化合物溶液的非线性光学响应，详细地考察其结构与非线性光学性质的关系。期望通过本课题的研究，扩大对含硫杂核金属簇合物的合成化学和结构化学的了解，扩大对非线性光学材料的研究范围，为开发出优良性能的三阶非线性光学材料打下良好的基础。