Assembly of new Mo/Cu/S clusters from [Et4N][Tp*MoS(S4)] and Cu(I) salts: syntheses, structures and third-order nonlinear optical properties.
Assembly of new Mo/Cu/S clusters from [Et4N][Tp*MoS(S4)] and Cu(I) salts: syntheses, structures and third-order nonlinear optical properties.
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DOI：
10.1039/c3dt50759a
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发表时间：
2013-06
影响因子：
4
通讯作者：
Zhi‐Yuan Zhang;Wei-Jie Gong;Fan Wang;Min-min Chen;Li-Kuan Zhou;Zhi‐Gang Ren;Zhenrong Sun;J. Lang
中科院分区：
文献类型：
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作者：
Zhi‐Yuan Zhang;Wei-Jie Gong;Fan Wang;Min-min Chen;Li-Kuan Zhou;Zhi‐Gang Ren;Zhenrong Sun;J. Lang
[Et4N][Tp*MoS(S)4] (Tp* = 氢化三(3,5-二甲基吡唑-1-基)硼酸盐) (1) 与 3 当量的反应CuX (X = Cl, Br, I, CN) 或 [Cu(MeCN)4]ClO4 在 CH2Cl2-MeCN 或 CH2Cl2-DMF 中得到 [Et4N]2[Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] (2), [Et4N][Tp*Mo(μ3-S)3(CuX)3] (3: X = Br; 4: X = I)、[Et4N][Tp*MoO(μ-S)2(CuX)]（5：X = I；6：X = CN）和 [Tp*Mo(μ3-S)3Cu3(μ3-S')]4 (7)。通过元素分析、红外光谱、紫外-可见光谱、(1)H NMR、电喷雾离子质谱(ESI-MS)和X射线晶体学对化合物2-7进行了表征。 2的团簇二阴离子具有完整的类立方烷[Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)]结构，而3或4的阴离子由不完整的类立方烷[Tp*Mo(μ3-S)3(CuX)3]结构组成。 5或6的阴离子具有双核结构，其中一个[Tp*MoO(μ-S)2]部分和一个CuX单元通过一对μ-S原子连接。 7的结构可以被认为是一个超立方体，其八个角被四个不完整的立方烷状[Tp*Mo(μ3-S)3Cu3]片段和四个μ3-S'原子占据。通过飞秒简并四波混频 (DFWM) 技术，在 800 nm 处采用 80 fs 脉冲宽度，研究了 2-6 在 DMF 中的三阶非线性光学 (NLO) 特性。化合物2-6表现出良好的NLO性能，其NLO响应相对于1有所增强。
Reactions of [Et4N][Tp*MoS(S)4] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with 3 equiv. of CuX (X = Cl, Br, I, CN) or [Cu(MeCN)4]ClO4 in CH2Cl2-MeCN or CH2Cl2-DMF afforded [Et4N]2[Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] (2), [Et4N][Tp*Mo(μ3-S)3(CuX)3] (3: X = Br; 4: X = I), [Et4N][Tp*MoO(μ-S)2(CuX)] (5: X = I; 6: X = CN) and [Tp*Mo(μ3-S)3Cu3(μ3-S')]4 (7). Compounds 2-7 were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, electrospray ion mass spectra (ESI-MS) and X-ray crystallography. The cluster dianion of 2 has a complete cubane-like [Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] structure while the anion of 3 or 4 consists of an incomplete cubane-like [Tp*Mo(μ3-S)3(CuX)3] structure. The anion of 5 or 6 has a binuclear structure, in which one [Tp*MoO(μ-S)2] moiety and one CuX unit are linked by a pair of μ-S atoms. The structure of 7 may be considered as a supercube whose eight corners are occupied by four incomplete cubane-like [Tp*Mo(μ3-S)3Cu3] fragments and four μ3-S' atoms. The third-order nonlinear optical (NLO) properties of 2-6 in DMF were investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80 fs pulse width at 800 nm. Compounds 2-6 exhibited good NLO performances and their NLO responses were enhanced relative to that of 1.