Syntheses and Characterization of Several Copper‐halo Clusters

The hydrothermal reaction of CuBr 2 and CuBr with phen·H 2 O (phen=1,10‐phenanthroline) in a molar ratio of 1:1:1.5 gave birth to the first copper‐halo cationic cluster [Cu 2 II Cu 2 I Br 4 (phen) 4 ] 2+ ( 1 ) with tetranuclear anionic cluster [Cu 4 Br 6 ] 2‐ . Changing the precursors or their molar ratios, two mononuclear complexes [Cu(phen) 2 Br]Br·H 2 O ( 2 ) and [Ni(phen) 3 ][CuCl 2 ] 2 ( 3 ) as well as two unusual copper‐halo chains found in polymers [Cu 2 Br 2 (phen)] ∞ ( 4 ) and [Cu II Cu 3 I Br 2 I 3 (phen) 2 ] ∞ ( 5 ) were obtained. The (Cu 2 Br 2 ) ∞ chain of 4 looks like a linear array of hexagons based on fused Cu 3 Br 3 units, and the linear (Cu 3 I 3 Br ‐ ) N , N′ chain of 5 is an alternate combination of the rhombic Cu 2 I 2 cores and the Cu 4 I 4 Br 2 2‐ units. In addition, the hydrothermal reaction of CuBr 2 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 (α 2 >0) and self‐defocusing performance( n 2 <0).