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 ![[italic v (to differentiate from Times ital nu)]](https://www.rsc.org/images/entities/char_e0f5.gif)
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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