The first heterothiometallic complex of bis(diphenylthiophosphoryl)amide [(Ph2PS)2N]?: synthesis, crystal structure and nonlinear optical effects of the dodecanuclear cluster compound (Et4N)4[Mo4Cu8O4S12{(Ph2PS)2N}4]

New Journal of Chemistry Pub Date: 2001-06-08 DOI: 10.1039/B102238P

Abstract

The heterothiometallic cluster compound (Et4N)4[Mo4Cu8O4S12{(Ph2PS)2N}4] has been synthesized by the reaction of (Et4N)2[Mo2Cu6Br2I4O2S6] with K[(Ph2PS)2N] in CH3CN. An X-ray structure determination revealed that the anionic cluster consists of a square [Mo4Cu4O4S12]? framework which is formed by four MoOS32? building blocks linked [italic v (to differentiate from Times ital nu)]ia four Cu atoms, and four pendant Cu[Ph2P(S)NP(S)Ph2] units, each bound to one of the corner MoOS3 moieties. The structure can also be regarded as a tetramer of nest-shaped MoCu3OS3[(Ph2PS)2N] monomers co-polymerized by sharing the limbic Cu atoms. The [Ph2P(S)NP(S)Ph2]? ligand adopts a classical S,S′-chelating mode, resulting in the formation of a six-membered CuS2P2N ring of chair configuration. The nonlinear optical (NLO) properties were studied with an 8 ns pulsed laser at 532 nm. Its optical response to the incident light exhibits good optical absorptive and refractive effects, with α2 ?=?1.2 × 10?11 m W?1 and n2 ?=? ?2.04 × 10?18 m2 W?1 for a 1.2 × 10?4 mol dm?3 DMF solution.

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