College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, Jilin 130023, China

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)₂-Br]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^－)_¥ 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.)