Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
Inorg Chem. 2011 May 16;50(10):4493-502. doi: 10.1021/ic200147d. Epub 2011 Apr 8.
Treatment of [Et(4)N][TpWS(3)] (1) (Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(TpWS(2))(2)(μ-S(2))] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH(2)Cl(2) or CHCl(3) formed three neutral W/Cu/S clusters {Tp*W(μ(3)-S)(3)Cu(3)(μ-Cl)}(2)Cu(μ-Cl)(2)(μ(7)-Cl)(MeCN) (3), [{TpW(μ(3)-S)(3)Cu(3)}(2)Br(μ-Br)(2)(μ(4)-Br)(MeCN)] (4), and [{TpW(μ(3)-S)(3)Cu(3)}(2){Cu(2)(μ-I)(4)(μ(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et(4)NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et(4)N][{TpW(μ(3)-S)(3)Cu(3)X}(2)(μ-X)(2)(μ(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR, UV-vis, (1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS(2)] fragments in which two W atoms are connected by one S(2)(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two Tp*W(μ(3)-S)(3)Cu(3) dications are linked via a μ(7)-Cl(-) bridge, two μ-Cl(-) bridges, and a Cu(MeCN)(μ-Cl)(2) bridge. For 4, one Tp*W(μ(3)-S)(3)Cu(3)(MeCN) dication and one Tp*W(μ(3)-S)(3)Cu(3)Br cation are linked via a μ(4)-Br(-) and two μ-Br(-) bridges. For 5, the two Tp*W(μ(3)-S)(3)Cu(3) dications are bridged by a linear (μ-I)(2)Cu(μ(3)-I)(2)Cu(μ-I)(2) species. For 6 and 7, two Tp*W(μ(3)-S)(3)Cu(3)X cations are linked by a μ(4)-X(-) and two μ-X(-) bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH(2)Cl(2) were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.
治疗[Et(4)N][TpWS(3)]（1）（Tp=氢代三（3,5-二甲基吡唑-1-基）硼酸盐）与 2 当量的 AgSCN 在 MeCN 中得到一种新型中性化合物[（TpWS(2))(2)(μ-S(2))]（2）。2 与过量的 CuX（X = Cl、Br、I）在 MeCN 和 CH(2)Cl(2)或 CHCl(3)中的反应形成三个中性 W/Cu/S 簇 [{TpW(μ(3)-S)(3)Cu(3)(μ-Cl)}(2)Cu(μ-Cl)(2)(μ(7)-Cl)(MeCN)]（3），[{TpW(μ(3)-S)(3)Cu(3)}(2)Br(μ-Br)(2)(μ(4)-Br)(MeCN)]（4）和[{TpW(μ(3)-S)(3)Cu(3)}(2){Cu(2)(μ-I)(4)(μ(3)-I)(2)}]（5），分别。另一方面，2 与 CuX（X = Cl、Br）在存在 Et(4)NX（X = Cl、Br）的情况下产生两个阴离子 W/Cu/S 簇[Et(4)N][{TpW(μ(3)-S)(3)Cu(3)X}(2)(μ-X)(2)(μ(4)-X)]（6：X = Cl；7 X = Br）。2-7 通过元素分析、IR、UV-vis、(1)H NMR、电喷雾电离（ESI）质谱和单晶 X 射线晶体学进行了表征。2 的二聚体结构可以看作是两个[TpWS(2)]片段，其中两个 W 原子通过一个 S(2)(2-)二阴离子连接。化合物 3-7 均具有独特的卤化物桥联双立方笼状结构。对于 3，两个Tp*W(μ(3)-S)(3)Cu(3)二阳离子通过μ(7)-Cl(-)桥、两个μ-Cl(-)桥和[Cu(MeCN)(μ-Cl)(2)]+桥连接。对于 4，一个Tp*W(μ(3)-S)(3)Cu(3)(MeCN)二阳离子和一个Tp*W(μ(3)-S)(3)Cu(3)Br阳离子通过μ(4)-Br(-)和两个μ-Br(-)桥连接。对于 5，两个Tp*W(μ(3)-S)(3)Cu(3)二阳离子通过线性(μ-I)(2)Cu(μ(3)-I)(2)Cu(μ-I)(2)物种桥接。对于 6 和 7，两个Tp*W(μ(3)-S)(3)Cu(3)X阳离子通过μ(4)-X(-)和两个μ-X(-)桥（X = Cl、Br）连接。此外，还通过飞秒简并四波混频（DFWM）技术研究了 2-7 在 MeCN/CH(2)Cl(2)中的三阶非线性光学（NLO）性质。
