title: Construction of new heteroselenometallic clusters: formation of crownlike [Et4N]4[(mu5-WSe4)(CuI)5(mu-I)2] and octahedral polymeric [(mu6-WSe4)Cu6I4(py)4]n from planar [Et4N]4[(mu4-WSe4)Cu4I6] with additional faces.
abstract: 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).
authors.affiliation: Department of Applied Chemistry, Anhui University of Technology, Maanshan, Anhui 243002, P. R. China. zhangqf@ahut.edu.cn
authors.forename: Qian-Feng
authors.initials: QF
authors.lastname: Zhang
authors.forename: Zhan
authors.initials: Z
authors.lastname: Yu
authors.forename: Jihai
authors.initials: J
authors.lastname: Ding
authors.forename: Yinglin
authors.initials: Y
authors.lastname: Song
authors.forename: Alexander
authors.initials: A
authors.lastname: Rothenberger
authors.forename: Dieter
authors.initials: D
authors.lastname: Fenske
authors.forename: Wa-Hung
authors.initials: WH
authors.lastname: Leung
mesh_terms: D000838:Anions / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D018036:Selenium Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D000838:Anions; D009942:Organometallic Compounds; D018036:Selenium Compounds; D003300:Copper