几个金属卤素簇的合成与性能研究

The hydrothermal reaction of CuBr2 and CuBr with phen·H2O （phen= 1,10-phenanthroline） in a molar ratio of 1：1：1.5 gave birth to the first copper-halo cationic cluster [Cu2^Ⅱ Cu2^Br4 （phen）4 ] ^2＋（1） with tetranuclear anionic cluster [Cu4Br6]^2-. Changing the precursors or their molar ratios, two mononuclear complexes [Cu（phen）2Br]Br·H2O （2） and [Ni（phen）3][CuCl2]2 （3） as well as two unusual copper-halo chains found in polymers [Cu2Br2（phen）]∞ （4） and [Cu^ⅡCu3^ⅠBr2Ⅰ3 （phen）2 ]∞ （5） were obtained. The （Cu2Br2）∞ chain of 4 looks like a linearar ray of hexagons based on fused Cu3Br3 units, and the linear （Cu3Ⅰ3Br^-）∞ chain of 5 is an alternate combination of the rhombic Cu2I2 cores and the Cu4I4Br2^2- units. In addition, the hydrothermal reaction of CuBr2 with NA（NA=nicotinic acid） or INA （INA =isonicotinic acid） resulted in the syntheses of two compounds [CuBr（NA）] （6） and [CuBr（INA）]∞（7） containing staircase chain. Among them the third-order non-linear optical properties of 2, 5, 6 and 7 were investigated and all exhibit the reverse saturable absorption （α2〉0） and self-defocusing performance （n2〈0）.

Syntheses and Characterization of Several Copper-halo Clusters

The hydrothermal reaction of CuBr₂ and CuBr with phen·H₂O (phen=1,10‐phenanthroline) in a molar ratio of 1:1:1.5 gave birth to the first copper‐halo cationic cluster [Cu₂^IICu₂^IBr₄(phen)₄]²⁺ ( 1 ) with tetranuclear anionic cluster [Cu₄Br₆]^2‐. Changing the precursors or their molar ratios, two mononuclear complexes [Cu(phen)₂Br]Br·H₂O ( 2 ) and [Ni(phen)₃][CuCl₂]₂ ( 3 ) as well as two unusual copper‐halo chains found in polymers [Cu₂Br₂(phen)]_∞ ( 4 ) and [Cu^IICu₃^IBr₂I₃(phen)₂]_∞ ( 5 ) were obtained. The (Cu₂Br₂)_∞chain of 4 looks like a linear array of hexagons based on fused Cu₃Br₃ units, and the linear (Cu₃I₃Br^‐)N,N′chain of 5 is an alternate combination of the rhombic Cu₂I₂ cores and the Cu₄I₄Br₂^2‐ units. In addition, the hydrothermal reaction of CuBr₂ with NA(NA=nicotinic acid) or INA (INA=isonicotinic acid) resulted in the syntheses of two compounds [CuBr(NA)] ( 6 ) and [CuBr(INA)]_∞ ( 7 ) containing staircase chain. Among them the third‐order non‐linear optical properties of 2 , 5 , 6 and 7 were investigated and all exhibit the reverse saturable absorption (α₂>0) and self‐defocusing performance(n₂<0).