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Syntheses and Characterization of Several Copper-halo Clusters

Syntheses and Characterization of Several Copper-halo Clusters
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摘要 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). 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).
出处 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2005年第8期1030-1036,共7页 中国化学(英文版)
基金 Project supported by the National Natural Science Foundation of China(Nos. 20271021 and 20333070).
关键词 copper-halo cluster 1 10-PHENANTHROLINE hydrothermal synthesis crystal structure non-linear optics copper-halo cluster, 1,10-phenanthroline, hydrothermal synthesis, crystal structure, non-linear optics
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