First optical non-linearity study on Group 6–Group 10 sulfido mixed-metal complexes, synthesis and crystal structure of [NEt4][PdWS4(S2CNC4H8)] and [NEt4]2[PdW2S8]

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De-Liang Long, Wing-Tak Wong, Shu Shi, Xin-Quan Xin and Jin-Shun Huang


Abstract

Two Group 6–Group 10 sulfido mixed-metal complexes, [NEt4][PdWS4(S2CNC4H8)] 1 and [NEt4]2[PdW2S8] 2, have been synthesized via reactions of [Pd(S2CNC4H8)2] with [NH4]2[WS4] and NEt4Cl 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 (n2 = –6.8 × 10–18 m2 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 (n2 = –7.5 × 10–18 m2 W–1, as measured with a 1.6 × 10–3 mol dm–3 acetonitrile solution) and optical non-linear absorption (α2 = 3.5 × 10–11 m W–1).


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