Construction of New Heteroselenometallic Clusters: Formation of Crownlike [Et<sub>4</sub>N]<sub>4</sub>[(μ<sub>5</sub>-WSe<sub>4</sub>)(CuI)<sub>5</sub>(μ-I)<sub>2</sub>] and Octahedral Polymeric [(μ<sub>6</sub>-WSe<sub>4</sub>)Cu<sub>6</sub>I<sub>4</sub>(py)<sub>4</sub>]<i><sub>n</sub></i> from Planar [Et<sub>4</sub>N]<sub>4</sub>[(μ<sub>4</sub>-WSe<sub>4</sub>)Cu<sub>4</sub>I<sub>6</sub>] with Additional Faces
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The coplanar cluster compound [Et4N]4[(μ4-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 [Et4N]I. Treatment of 1 with pyridine (py) in dry MeCN gave the neutral cluster [(μ4-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 [(μ3-WOSe3)Cu3(py)3(μ-I)]n (3) containing a nest-shaped OWSe3Cu3 core and a terminal WO bond. The interaction of cluster 1 with excess PPh3 in CH2Cl2 gave [(μ3-WSe4)Cu3(PPh3)3(μ3-I)] (4) which has a cubanelike SeWSe3Cu3I core. Treatment of 1 with 1 equiv of CuI in dimethyl sulfoxide (DMSO) yielded [Et4N]4[(μ5-WSe4)(CuI)5(μ-I)2] (5) which has a crownlike 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, [(μ6-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.
