Stepwise reactions of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 1–4 equiv. of CuNCS (and Et4NBr in the case of three equiv. of CuNCS) afforded the [1 + 1] to [1 + 4] addition products [Et4N][Tp*WS(μ-S)2(CuNCS)]·0.5CH2Cl2 (2·0.5CH2Cl2), [Et4N][Tp*W(μ3-S)(μ-S)2(CuNCS)2]·ClCH2CH2Cl (3·ClCH2CH2Cl), [Et4N]2[Tp*W(μ3-S)3(CuNCS)3(μ3-Br)]·1.5aniline (4·1.5aniline), and {[Et4N][Tp*W(μ3-S)3(Cu-μ-SCN)3(Cu-μ3-NCS)]}n (5). Compounds 2–5 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and single-crystal X-ray crystallography. The cluster anion of 2 contains a [WS2Cu] core formed by addition of one CuNCS group onto the [Tp*WS3] species. The cluster anion of 3 has a butterfly-shaped [WS3Cu2] core constructed by addition of two CuNCS groups onto the [Tp*WS3] species. The cluster dianion of 4 consists of a cubane-like [Tp*WS3Cu3(μ3-Br)] core assembled by addition of three CuNCS groups onto the [Tp*WS3] species followed by filling a μ3-Br into the void of the incomplete cubane-like [Tp*WS3(CuNCS)3] fragment. 5 has a 2D cluster-supported layer network in which each [Tp*WS3Cu3] core acting as a pyramidal 3-connecting node interconnects with the [Cu(NCS)4] units through thiocyanate bridges. In addition, the third-order nonlinear optical (NLO) performances of 2–5 in DMF were also investigated by Z-scan techniques.
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