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crystal structure tungsten silver sulfido arsine; tungsten silver sulfido arsine hexanuclear complex; nonlinear optical tungsten silver sulfido arsine; electrochem tungsten silver sulfido arsine complex; cluster tungsten silver sulfido arsine
W2S8Ag4(AsPh3)4 was prepd. by gently heating the solid-state reaction mixt. of (NH4)2WS4, AgBr, and AsPh3. Its structure was detd. by single-crystal x-ray diffraction. The compd. crystallizes in the triclinic space group P-1, with a 12.440(2), b 13.793(5) angstrom,c 11.513(3) angstrom, a 96.41(2), b 108.10(2), g 93.52(2)degree, and Z = 2; R = 0.041, Rw = 0.060. The structure can be described as a hexagonal prism shaped cage that consists of two identical butterfly shaped WS4(AgAsPh3)2 segments. These segments are interconnected by four relatively long Ag-S bonds. The electronic spectrum, cyclic voltammogram, and x-ray photoelectron spectrum of the cluster were obtained. Nonlinear optical (NLO) properties of the cluster were studied with 7-ns pulsed laser at 532 nm. The cluster exhibits both optical self-focusing and optical nonlinear absorption (n2eff = 5.9 x 10-17 m2 W-1; a2eff = 2.8 x 10-9 m W-1; examd. in a 1.3 x 10-4 mol dm-3 MeCN soln.). The corresponding effective 3rd-order NLO susceptibility (c(3)eff) of the cluster is 1.7 x 10-10 esu. These nonlinear optical properties of the cluster are compared with those of butterfly shaped clusters and those of other known NLO materials.
Research papers (academic journals)
