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Title: Stepwise addition of CuNCS onto [Et(4)N][Tp*WS(3)]: design, syntheses, structures and third-order nonlinear optical properties.
Author: Wei ZH, Li HX, Ren ZG, Lang JP, Zhang Y, Sun ZR.
Journal: Dalton Trans; 2009 May 14; (18):3425-33. PubMed ID: 19381405.
Abstract:
Stepwise reactions of [Et(4)N][Tp*WS(3)] () (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 1-4 equiv. of CuNCS (and Et(4)NBr in the case of three equiv. of CuNCS) afforded the [1 + 1] to [1 + 4] addition products [Et(4)N][Tp*WS(mu-S)(2)(CuNCS)].0.5CH(2)Cl(2) (.0.5CH(2)Cl(2)), [Et(4)N][Tp*W(mu(3)-S)(mu-S)(2)(CuNCS)(2)].ClCH(2)CH(2)Cl (.ClCH(2)CH(2)Cl), [Et(4)N](2)[Tp*W(mu(3)-S)(3)(CuNCS)(3)(mu(3)-Br)].1.5aniline (.1.5aniline), and {[Et(4)N][Tp*W(mu(3)-S)(3)(Cu-mu-SCN)(3)(Cu-mu(3)-NCS)]}(n) (). Compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, and single-crystal X-ray crystallography. The cluster anion of contains a [WS(2)Cu] core formed by addition of one CuNCS group onto the [Tp*WS(3)] species. The cluster anion of has a butterfly-shaped [WS(3)Cu(2)] core constructed by addition of two CuNCS groups onto the [Tp*WS(3)] species. The cluster dianion of consists of a cubane-like [Tp*WS(3)Cu(3)(mu(3)-Br)] core assembled by addition of three CuNCS groups onto the [Tp*WS(3)] species followed by filling a mu(3)-Br into the void of the incomplete cubane-like [Tp*WS(3)(CuNCS)(3)] fragment. has a 2D cluster-supported layer network in which each [Tp*WS(3)Cu(3)] 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 in DMF were also investigated by Z-scan techniques.

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