First optical non-linearity study on Group 6-Group 10 sulfido mixed-metal complexes, synthesis and crystal structure of [NEt 4][PdWS 4(S 2CNC 4H 8)] and [NEt 4] 2[PdW 2S 8]

Abstract

Two Group 6-Group 10 sulfido mixed-metal complexes, [NEt 4][PdWS 4(S 2CNC 4H 8)] 1 and [NEt 4] 2[PdW 2S 8] 2, have been synthesized via reactions of [Pd(S 2CNC 4H 8) 2] with [NH 4] 2[WS 4] and NEt 4Cl in different molar ratios in dichloromethane. X-Ray crystallographic structure determinations revealed that palladium in 1 is co-ordinated by a pyrrolidinecarbodithioate and a tetrathiotungstate, while in 2 it is co-ordinated by two tetrathiotungstates symmetrically. Both dithiocarbamate and tetrathiotungstate act as bidentate ligands through two sulfur atoms chelating palladium. The Pd-W distances are 2.8669(7) and 2.9008(5) Å in 1 and 2, respectively. Non-linear optical properties of the compounds were studied with a 7 ns pulsed laser at 532 nm. Compound 1 exhibits mainly optical self-defocusing (n 2 = -6.8 × 10 -18 m 2 W -1 as measured with a 1.0 × 10 -3 mol dm -3 acetonitrile solution) with negligible non-linear absorption. Compound 2 exhibits both optical self-defocusing (n 2 = -7.5 × 10 -18 m 2 W -1, as measured with a 1.6 × 10 -3 mol dm -3 acetonitrile solution) and optical non-linear absorption (α 2 = 3.5 × 10 -11 m W -1).