Synthesis, crystal structure and nonlinear optical properties of two new cluster compounds: [WCu3S4(PPH3)3{S2P(OCH2Ph2}] and [WAg3OS3(PH3P)3{S2P(OPri)2}]

Abstract

Two new O,O′-dialkyl dithiophosphate-containing sulfido clusters, [WCu3S4(PPh3)3{S2P(OCH2Ph)2}] 1 and [WAg3OS3(Ph3P)3{S2P(OPri)2}] 2, were synthesized through reactions of [NH4]2[WS4] with [CuS2P(OCH2Ph)2] and [NH4]2[WOS3] with [AgS2P(OPri)2], respectively. Their crystal structures and nonlinear optical properties are reported. The X-ray crystallographic structure of 1 is an incomplete cubane-like structure, the dithiophosphate ligand adopts a triply bridging role, employing two sulfur atoms to coordinate to the three Cu atoms: one sulfur atom binds to one Cu atom, another sulfur atom to two other Cu atoms. The structure of 2 contains a half-open cubane-like cluster core, the dithiophosphate ligand acts as a bidentate ligand and the two S atoms of the di-isopropyl dithiophosphato ligand coordinate to two Ag atoms, respectively. Using a Z-scan technique with 532 nm laser radiation, both the real and imaginary parts of third-order nonlinear susceptibility of clusters 1 and 2 were determined.