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]

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 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.