Synthesis, crystal structure and nonlinear optical properties of two new cluster compounds: [WCu3S4(PPh3)3{S2P(OCH2Ph)2}] and [WAg3OS3(Ph3P)3{S2P(OPri)2}]

Two new O , O ′-dialkyl dithiophosphate-containing sulfido clusters, [WCu 3 S 4 (PPh 3 ) 3 {S 2 P(OCH 2 Ph) 2 }] 1 and [WAg 3 OS 3 (Ph 3 P) 3 {S 2 P(OPr i ) 2 }] 2 , were synthesized through reactions of [NH 4 ] 2 [WS 4 ] with [CuS 2 P(OCH 2 Ph) 2 ] and [NH 4 ] 2 [WOS 3 ] with [AgS 2 P(OPr i ) 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.