Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, PR China.
Dalton Trans. 2011 Sep 7;40(33):8391-8. doi: 10.1039/c1dt10685f. Epub 2011 Jul 22.
Reactions of the preformed cluster (η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)(2) (1) with two tetraphosphine ligands, 1,4-N,N,N',N'-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) and N,N,N',N'-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda), produced two bicyclic clusters {(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(L)}(ClO(4))(4) (3: L = dpppda; 4: L = dppeda). Analogous reactions of 1 or (η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)(2) (2) with two N,P mixed ligands, N,N-bi(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) and N-diphenylphosphanylmethyl-4-aminopyridine (dppmapy), afforded two monocyclic clusters {(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(L)(2)}X(4) (5: L = bdppmapy, X = ClO(4); 6: L = dppmapy, X = PF(6)). Compounds 3-6 were fully characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H and (31)P{(1)H} NMR spectra, ESI-MS and single-crystal X-ray crystallography. In the tetracations of 3-6, two cubane-like [Mo(2)(μ(3)-S)(4)Cu(2)] cores are linked either by one dpppda or dppeda bridge to form a bicyclic structure or by a pair of bdppmapy or dppmapy bridges to afford a monocyclic structure. The third-order nonlinear optical (NLO) properties of 1 and 3-6 in MeCN were also investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 50 fs pulse width at 800 nm. Compounds 3-6 exhibited enhanced third-order NLO performances relative to that of 1.
(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)(2) (1) 与两种四膦配体，1,4-N,N,N',N'-四(二苯膦基甲基)苯二胺(dpppda)和 N,N,N',N'-四(二苯膦基甲基)乙二胺(dppeda)反应，生成了两个二环簇{(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(L)}(ClO(4))(4) (3: L = dpppda; 4: L = dppeda)。类似地，1 或(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(MeCN)(2)(2) (2) 与两种 N,P 混合配体，N,N-双(二苯膦基甲基)-2-氨基吡啶(bdppmapy)和 N-二苯膦基甲基-4-氨基吡啶(dppmapy)反应，得到了两个单核簇{(η(5)-C(5)Me(5))(2)Mo(2)(μ(3)-S)(4)Cu(2)(L)(2)}X(4) (5: L = bdppmapy, X = ClO(4); 6: L = dppmapy, X = PF(6))。化合物 3-6 均通过元素分析、IR 光谱、UV-vis 光谱、(1)H 和(31)P{(1)H} NMR 光谱、ESI-MS 和单晶 X 射线晶体学进行了充分表征。在 3-6 的四阳离子中，两个类似立方烷的[Mo(2)(μ(3)-S)(4)Cu(2)]核通过一个 dpppda 或 dppeda 桥连接形成二环结构，或者通过一对 bdppmapy 或 dppmapy 桥连接形成单核结构。还通过 50 fs 脉宽、800nm 的飞秒简并四波混频(DFWM)技术研究了 1 和 3-6 在 MeCN 中的三阶非线性光学(NLO)性质。与 1 相比，化合物 3-6 表现出增强的三阶 NLO 性能。
