A half-open cage-shaped cluster, (NEt4)3[WOS3(CuBr)3(μ 2-Br)]·2H2O: Synthesis, structure, and nonlinear optical properties

Abstract

Reaction of (NH4)2WO2S2, CuBr, and Et4NBr in solid state produced (NEt4)3[WOS3(CuBr)]·2H2O. Single-crystal X-ray diffraction data reveal that the anionic cluster [WOS3(CuBr)3(μ-Br)]3- has a half-open cage structure, an intermediate structure between cubic-cage and nest structures. Nonlinear optical (NLO) properties of the cluster were studied with a 7-ns pulsed laser at 532 nm. The cluster exhibits both optical self-focusing and optical nonlinear absorption stemed from a fluence dependent process (n2 eff = 1.1 × 10-16 m2 W-1, α2 eff = 6.0 × 10-10 m W-1, when measured with a 9.1 × 10-4 mol dm-3 acetonitrile solution). The corresponding effective NLO susceptibilities (χ(3) eff) of the cluster is 2.6 × 10-10 esu. These nonlinear optical properties of the cluster were compared with those of cubic-cage-shaped and nest-shaped clusters and those of other known NLO materials. © 1995 American Chemical Society.