Synthesis and nonlinear optical absorptive and refractive properties of several novel nest-shaped clusters, and crystal structures of [MoI(bPy)(2)][MoOS3Cu3I2(bPy)] and [MoOS3Cu3I(Phen)(2)]

Nest-shaped clusters [MI(bPy)(2)][MOS3Cu3I2(bPy)] (M = Mo, 1; M = W, 2) wer e synthesized by the treatment of (NH4)(2)MO2S2, Cut and Et,NI with 2,2'-bi pyridyl (bPy) in CH,CN. Both clusters show a very interesting structure, an d consist of two parts: a nest-shaped structural unit [MOS3Cu3I2(bPy)](-) a nd complex ion [MI(bPy)(2)](+). By the reaction of [Et4N](4)[Mo2O2S6Cu6I6] with Phen (1,10-phenanthroline), or bPy, or bMe-bPy (4,4'-dimethyl-2,2'-bip yridyl), we prepared nest-shaped clusters [MoOS3Cu3IR2] (R = Phen, 3; R = b Py, 4; R = bMe-bPy, 5). The crystal structures of [MoI(bPy)(2)][MoOS3Cu3I2( bPy)] (1) and [MoOS3-Cu3I(Phen)(2)] (3) were characterized by X-ray diffrac tion. Their nonlinear optical (NLO) properties were studied with a 7-ns pul sed laser at 532 nm. Cluster 1 has large NLO absorption and NLO refraction, its alpha(2) and n(2) values were calculated as 3.0 x 10(-10) m W-1 and -3 .0 x 10(-17) m(2) W-1 in a 3.4 x 10(-5) mol dm(-3) DMF solution, respective ly. Cluster 2 only exhibits very strong NLO absorptive property, its alpha( 2) value is 1.0 x 10(-9) m W-1 when measured in a 4.8 x 10(-5) mol dm(-3) D MF solution. Clusters 4 and 5 have strong NLO absorption too. Their alpha(2 ) values were calculated as 7 x 10(-11) m W-1 and 3.5 x 10(-10) m W-1, resp ectively. Cluster 3 only shows moderate NLO absorption, its alpha(2) value is similar to 10(-11) m W-1. (C) 2000 Elsevier Science S.A. All rights rese rved.