Zhang Qian-Feng, Yu Zhan, Ding Jihai, Song Yinglin, Rothenberger Alexander, Fenske Dieter, Leung Wa-Hung
Department of Applied Chemistry, Anhui University of Technology, Maanshan, Anhui 243002, P. R. China.
Inorg Chem. 2006 Jun 26;45(13):5187-95. doi: 10.1021/ic060161p.
The coplanar cluster compound [Et4N]4[(mu4-WSe4)Cu4I6] (1) was prepared from reaction of [Et4N]2[WSe4] with 4 equiv of CuI in N,N-dimethylformamide (DMF) solution in the presence of [Et(4)N]I. Treatment of 1 with pyridine (py) in dry MeCN gave the neutral cluster [(mu4-WSe4)Cu4(py)6I2] (2) in good yield. Recrystallization of 1 from py/i-PrOH resulted in the reorganization of the coplanar WSe4Cu4 core and the formation of a neutral polymeric cluster [(mu3-WOSe3)Cu3(py)3(mu-I)]n (3) containing a nest-shaped OWSe3Cu3 core and a terminal W=O bond. The interaction of cluster 1 with excess PPh3 in CH3Cl3 gave [(mu3-WSe4)Cu3(PPh3)3(mu3-I)] (4) which has a cubanelike SeWSe3Cu3I core. Treatment of 1 with 1 equiv of CuI in dimethyl sulfoxide (DMSO) yielded [Et4N]4[(mu5-WSe4)(CuI)5(mu-I)2] (5) which has a crown-like core structure. Treatment of 1 in DMF with 2 equiv of CuI in the presence of py resulted in the formation of a two-dimensional polymeric cluster, [(mu6-WSe4)Cu6I4(py)4]n (6), consisting of an octahedral WSe4Cu6 repeating unit. The solid-state structures of clusters 3, 5, and 6 have been further established by X-ray crystallography. The nonlinear optical properties of 6 have been also investigated. Cluster 6 was found to exhibit good photostability and a large optical limiting effect with the limiting threshold being ca. 0.3 J cm(-2).
共面簇合物[Et4N]4[(μ4-WSe4)Cu4I6] (1) 通过在[Et(4)N]I存在下，使[Et4N]2[WSe4]与4当量的CuI在N,N-二甲基甲酰胺(DMF)溶液中反应制备得到。在干燥的乙腈中用吡啶(py)处理1，以良好的产率得到中性簇合物[(μ4-WSe4)Cu4(py)6I2] (2)。从py/异丙醇中对1进行重结晶导致共面的WSe4Cu4核发生重组，并形成了一个中性聚合物簇合物[(μ3-WOSe3)Cu3(py)3(μ-I)]n (3)，其包含一个巢状的OWSe3Cu3核和一个端基W=O键。簇合物1与过量的三苯基膦在氯仿中相互作用得到[(μ3-WSe4)Cu3(PPh3)3(μ3-I)] (4)，其具有类似立方烷的SeWSe3Cu3I核。在二甲基亚砜(DMSO)中用1当量的CuI处理1得到[Et4N]4[(μ5-WSe4)(CuI)5(μ-I)2] (5)，其具有冠状核结构。在DMF中，在py存在下用2当量的CuI处理1导致形成二维聚合物簇合物[(μ6-WSe4)Cu6I4(py)4]n (6)，其由八面体WSe4Cu6重复单元组成。簇合物3、5和6的固态结构已通过X射线晶体学进一步确定。还研究了6的非线性光学性质。发现簇合物6表现出良好的光稳定性和较大的光限幅效应，限幅阈值约为0.3 J cm(-2)。
