Zhang Qian-Feng, Ding Jihai, Yu Zhan, Song Yinglin, Rothenberger Alexander, Fenske Dieter, Leung Wa-Hung
Department of Applied Chemistry, Anhui University of Technology, Ma'anshan, Anhui 243002, P. R. China. zhangqf@ ahut.edu.cn
Inorg Chem. 2006 Oct 16;45(21):8638-47. doi: 10.1021/ic0610839.
Treatment of [Et4N]2[WSe4] with a 1:1 mixture of AgNO3 and PCy3 (Cy = cyclohexyl) in the absence of iodide afforded a linear trinuclear compound [(mu-WSe4)(AgPCy3)2] (1). A similar reaction in the presence of iodide gave rise to the isolation of the cubanelike compound [(mu3-WSe4)Ag3(PCy3)3(mu3-I)] (2). Treatment of [Et4N]2[WSe4] with AgI in the presence of bidentate phosphine ligands bis(diphenylphosphino)amine (dppa) and bis(diphenylphosphino)methane (dppm) afforded the tetranuclear compounds [(mu3-WSe4)Ag3(mu-I)(mu-dppa)2] (3) and [(mu3-WSe4)Ag3(mu3-I)(mu-dppm)2] (4), respectively, which exhibit an open butterfly configuration. A novel hexanuclear cluster compound [(mu3-WSe4)2Ag4(mu-dppm)3] (5) was obtained from interaction of [Et4N]2[WSe4] with AgNO3 and dppm in the absence of iodide source. The above cluster compounds are electrically neutral and air-stable in both solution and the solid state and have been characterized by electronic, infrared, mass, and NMR spectroscopies. The solid-state structures of five cluster compounds have been established by X-ray crystallography. The nonlinear optical properties of compounds 4 and 5 were examined by z-scan techniques with 7 ns pulses at 532 nm. The optical limiting effects of compounds 1, 2, 4, and 5 were determined and compared with related argentoselenometallic compounds.
在不存在碘化物的情况下，将[Et4N]2[WSe4]与AgNO3和PCy3（Cy = 环己基）的1:1混合物反应，得到线性三核化合物[(μ-WSe4)(AgPCy3)2]（1）。在存在碘化物的情况下进行类似反应，分离得到立方烷状化合物[(μ3-WSe4)Ag3(PCy3)3(μ3-I)]（2）。在双齿膦配体双（二苯基膦基）胺（dppa）和双（二苯基膦基）甲烷（dppm）存在下，将[Et4N]2[WSe4]与AgI反应，分别得到四核化合物[(μ3-WSe4)Ag3(μ-I)(μ-dppa)2]（3）和[(μ3-WSe4)Ag3(μ3-I)(μ-dppm)2]（4），它们呈现出开放的蝴蝶构型。通过[Et4N]2[WSe4]与AgNO3和dppm在不存在碘源的情况下相互作用，得到了一种新型的六核簇合物[(μ3-WSe4)2Ag4(μ-dppm)3]（5）。上述簇合物在溶液和固态中均为电中性且空气稳定，并已通过电子、红外、质谱和核磁共振光谱进行了表征。五种簇合物的固态结构已通过X射线晶体学确定。通过z扫描技术，在532 nm下用7 ns脉冲对化合物4和5的非线性光学性质进行了研究。测定了化合物1、2、4和5的光限幅效应，并与相关的银硒金属化合物进行了比较。
