Syntheses and Characterization of Several Copper‐halo Clusters

AbstractThe 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 [Cu2IICu2IBr4(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 [CuIICu3IBr2I3(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 Cu4I4Br22‐ 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).