氢三（3,5 - 二甲基吡唑 - 1 - 基）硼酸酯（Tp）的三硫化钨配合物[Et(4)N][TpWS(3)]与CuX（X = Cl、NCS或CN）的反应：分离、结构及三阶非线性光学性质

Reactions of a tungsten trisulfido complex of hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp) [Et(4)N][TpWS(3)] with CuX (X = Cl, NCS, or CN): isolation, structures, and third-order NLO properties.

作者信息

Wang Jing, Sun Zhen-Rong, Deng Li, Wei Zheng-Hong, Zhang Wen-Hua, Zhang Yong, Lang Jian-Ping

机构信息

School of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215123, Jiangsu, PR China.

出版信息

Inorg Chem. 2007 Dec 24;46(26):11381-9. doi: 10.1021/ic701641h. Epub 2007 Nov 13.

DOI:10.1021/ic701641h

Abstract

Reactions of a tungsten trisulfido complex of hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) [Et4N][TpWS3] (1) with 3 equiv of CuCl in CHCl3 afforded a tetranuclear anionic cluster [Et4N][TpW(mu3-S)3(CuCl)3] (2), while that of 1 with 3 equiv of CuNCS in MeCN produced a decanuclear neutral cluster (major product) [TpW(mu3-S)3Cu3(mu-NCS)3(CuMeCN)]2 (3) along with a binuclear anionic cluster (minor product) [Et4N][TpWO(mu-S)2(CuNCS)] (4). Solvothermal reactions of 1 with 3 equiv of CuCN in MeCN at 80 degrees C for 48 h followed by slowly cooling it to ambient temperature gave rise to a polymeric cluster [TpW(mu3-S)(mu-S)2Cu2(MeCN)(mu-CN)]n (5). Compounds 2-5 were characterized by elemental analysis, IR, UV-vis, 1H NMR, and single-crystal X-ray crystallography. The cluster anion of 2 has a [TpWS3Cu3] incomplete cube with one Cl atom coordinated at each Cu center. 3 is composed of an unprecedented centrosymmetric W2Cu8 cluster core in which each void of the two single incomplete cubane-like [TpW(mu3-S)3Cu3(mu-NCS)]+ cations is partially filled with an extra [Cu(MeCN)(mu-NCS)2]- anion via a pair of Cu-mu-NCS-Cu bridges. The cluster anion of 4 contains one WS2Cu core that is formed by an oxidized [TpWO(mu-S)2] species and one CuNCS fragment. 5 consists of butterfly shaped [Tp*W(mu3-S)(mu-S)2Cu2(MeCN)] fragments that are interconnected via cyanide bridges to form a 1D spiral chain extending along the c axis. The successful synthesis of 2-5 from 1 suggests that 1 may be an excellent synthon to the W/Cu/S clusters. In addition, the third-order nonlinear optical (NLO) properties of 1-3 in solution were also investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80 fs pulse width at 800 nm. Although 2 was not detected to have NLO effects, 1 and 3 exhibited relatively good optical nonlinearities with the nonlinear refractive index n2 and the third-order nonlinear optical susceptibility chi(3) values being 0.79 x 10(-13) and 0.38 x 10(-14) esu (1) and 2.08 x 10(-13) and 1.00 x 10(-14) esu (3), respectively. The second-order hyperpolarizability gamma value for 3 (5.46 x 10(-32) esu) is ca. 5 times larger than that of its precursor 1.

摘要

氢三（3,5 - 二甲基吡唑 - 1 - 基）硼酸钨三硫代配合物（Tp*）[Et4N][TpWS3]（1）与3当量的CuCl在CHCl3中反应得到四核阴离子簇[Et4N][TpW(μ3 - S)3(CuCl)3]（2），而1与3当量的CuNCS在MeCN中反应生成十核中性簇（主要产物）[TpW(μ3 - S)3Cu3(μ - NCS)3(CuMeCN)]2（3）以及双核阴离子簇（次要产物）[Et4N][TpWO(μ - S)2(CuNCS)]（4）。1与3当量的CuCN在MeCN中于80℃溶剂热反应48小时，然后缓慢冷却至室温，得到聚合物簇[TpW(μ3 - S)(μ - S)2Cu2(MeCN)(μ - CN)]n（5）。化合物2 - 5通过元素分析、红外光谱、紫外可见光谱、1H核磁共振和单晶X射线晶体学进行表征。2的簇阴离子具有一个[TpWS3Cu3]不完全立方体，每个Cu中心配位有一个Cl原子。3由一个前所未有的中心对称W2Cu8簇核组成，其中两个单不完全类立方烷型[TpW(μ3 - S)3Cu3(μ - NCS)] + 阳离子的每个空隙通过一对Cu - μ - NCS - Cu桥被一个额外的[Cu(MeCN)(μ - NCS)2] - 阴离子部分填充。4的簇阴离子包含一个由氧化的[TpWO(μ - S)2]物种和一个CuNCS片段形成的WS2Cu核。5由蝴蝶形的[Tp*W(μ3 - S)(μ - S)2Cu2(MeCN)]片段组成，这些片段通过氰基桥相互连接形成沿c轴延伸的一维螺旋链。由1成功合成2 - 5表明1可能是合成W/Cu/S簇的优良合成子。此外，还通过飞秒简并四波混频（DFWM）技术在800nm波长、80fs脉冲宽度下研究了1 - 3在溶液中的三阶非线性光学（NLO）性质。虽然未检测到2有NLO效应，但1和3表现出相对良好的光学非线性，非线性折射率n2和三阶非线性光学极化率χ(3)值分别为0.79×10(-13)和0.38×10(-14) esu（1）以及2.08×10(-13)和1.00×10(-14) esu（3）。3的二阶超极化率γ值（5.46×10(-32) esu）约为其前体1的5倍。