title: Construction of halide-bridged tungsten-copper-sulfide double cubanelike clusters from a new precursor [(Tp*WS2)2(μ-S2)].
abstract: Treatment of [Et(4)N][Tp*WS(3)] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS(2))(2)(μ-S(2))] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH(2)Cl(2) or CHCl(3) formed three neutral W/Cu/S clusters [{Tp*W(μ(3)-S)(3)Cu(3)(μ-Cl)}(2)Cu(μ-Cl)(2)(μ(7)-Cl)(MeCN)](2) (3), [{Tp*W(μ(3)-S)(3)Cu(3)}(2)Br(μ-Br)(2)(μ(4)-Br)(MeCN)] (4), and [{Tp*W(μ(3)-S)(3)Cu(3)}(2){Cu(2)(μ-I)(4)(μ(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et(4)NX (X = Cl, Br) produced two anionic W/Cu/S clusters [Et(4)N][{Tp*W(μ(3)-S)(3)Cu(3)X}(2)(μ-X)(2)(μ(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR, UV-vis, (1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS(2)] fragments in which two W atoms are connected by one S(2)(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are linked via a μ(7)-Cl(-) bridge, two μ-Cl(-) bridges, and a [Cu(MeCN)(μ-Cl)(2)](+) bridge. For 4, one [Tp*W(μ(3)-S)(3)Cu(3)(MeCN)](2+) dication and one [Tp*W(μ(3)-S)(3)Cu(3)Br](+) cation are linked via a μ(4)-Br(-) and two μ-Br(-) bridges. For 5, the two [Tp*W(μ(3)-S)(3)Cu(3)](2+) dications are bridged by a linear [(μ-I)(2)Cu(μ(3)-I)(2)Cu(μ-I)(2)](4+) species. For 6 and 7, two [Tp*W(μ(3)-S)(3)Cu(3)X](+) cations are linked by a μ(4)-X(-) and two μ-X(-) bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH(2)Cl(2) were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.
authors.affiliation: Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
authors.forename: Li-Pei
authors.initials: LP
authors.lastname: Wei
authors.forename: Zhi-Gang
authors.initials: ZG
authors.lastname: Ren
authors.forename: Lian-Wen
authors.initials: LW
authors.lastname: Zhu
authors.forename: Wen-Yan
authors.initials: WY
authors.lastname: Yan
authors.forename: Sha
authors.initials: S
authors.lastname: Sun
authors.forename: Hui-Fang
authors.initials: HF
authors.lastname: Wang
authors.forename: Jian-Ping
authors.initials: JP
authors.lastname: Lang
authors.forename: Zhen-Rong
authors.initials: ZR
authors.lastname: Sun
mesh_terms: D001881:Borates / Q000138:chemical synthesis*; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D006219:Halogens / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D018716:Molecular Mimicry; D015394:Molecular Structure; D009591:Nitrogenase / Q000737:chemistry; D011355:Prodrugs / Q000138:chemical synthesis*; D011720:Pyrazoles / Q000138:chemical synthesis*; D018030:Silver Compounds / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013440:Sulfides / Q000737:chemistry; D014414:Tungsten / Q000737:chemistry*
chemical_list: D001881:Borates; D006219:Halogens; D011355:Prodrugs; D011720:Pyrazoles; D018030:Silver Compounds; D013440:Sulfides; D003300:Copper; D009591:Nitrogenase; D014414:Tungsten