title: Reactions of a tungsten trisulfido complex of hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) [Et(4)N][Tp*WS(3)] with CuX (X = Cl, NCS, or CN): isolation, structures, and third-order NLO properties.
abstract: Reactions of a tungsten trisulfido complex of hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) [Et4N][Tp*WS3] (1) with 3 equiv of CuCl in CHCl3 afforded a tetranuclear anionic cluster [Et4N][Tp*W(mu3-S)3(CuCl)3] (2), while that of 1 with 3 equiv of CuNCS in MeCN produced a decanuclear neutral cluster (major product) [Tp*W(mu3-S)3Cu3(mu-NCS)3(CuMeCN)]2 (3) along with a binuclear anionic cluster (minor product) [Et4N][Tp*WO(mu-S)2(CuNCS)] (4). Solvothermal reactions of 1 with 3 equiv of CuCN in MeCN at 80 degrees C for 48 h followed by slowly cooling it to ambient temperature gave rise to a polymeric cluster [Tp*W(mu3-S)(mu-S)2Cu2(MeCN)(mu-CN)]n (5). Compounds 2-5 were characterized by elemental analysis, IR, UV-vis, 1H NMR, and single-crystal X-ray crystallography. The cluster anion of 2 has a [Tp*WS3Cu3] incomplete cube with one Cl atom coordinated at each Cu center. 3 is composed of an unprecedented centrosymmetric W2Cu8 cluster core in which each void of the two single incomplete cubane-like [Tp*W(mu3-S)3Cu3(mu-NCS)]+ cations is partially filled with an extra [Cu(MeCN)(mu-NCS)2]- anion via a pair of Cu-mu-NCS-Cu bridges. The cluster anion of 4 contains one WS2Cu core that is formed by an oxidized [Tp*WO(mu-S)2] species and one CuNCS fragment. 5 consists of butterfly shaped [Tp*W(mu3-S)(mu-S)2Cu2(MeCN)] fragments that are interconnected via cyanide bridges to form a 1D spiral chain extending along the c axis. The successful synthesis of 2-5 from 1 suggests that 1 may be an excellent synthon to the W/Cu/S clusters. In addition, the third-order nonlinear optical (NLO) properties of 1-3 in solution were also investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80 fs pulse width at 800 nm. Although 2 was not detected to have NLO effects, 1 and 3 exhibited relatively good optical nonlinearities with the nonlinear refractive index n2 and the third-order nonlinear optical susceptibility chi(3) values being 0.79 x 10(-13) and 0.38 x 10(-14) esu (1) and 2.08 x 10(-13) and 1.00 x 10(-14) esu (3), respectively. The second-order hyperpolarizability gamma value for 3 (5.46 x 10(-32) esu) is ca. 5 times larger than that of its precursor 1.
authors.affiliation: School of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215123, Jiangsu, PR China.
authors.forename: Jing
authors.initials: J
authors.lastname: Wang
authors.forename: Zhen-Rong
authors.initials: ZR
authors.lastname: Sun
authors.forename: Li
authors.initials: L
authors.lastname: Deng
authors.forename: Zheng-Hong
authors.initials: ZH
authors.lastname: Wei
authors.forename: Wen-Hua
authors.initials: WH
authors.lastname: Zhang
authors.forename: Yong
authors.initials: Y
authors.lastname: Zhang
authors.forename: Jian-Ping
authors.initials: JP
authors.lastname: Lang
mesh_terms: D001881:Borates / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003486:Cyanides / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*; D017973:Tungsten Compounds / Q000737:chemistry*
chemical_list: D001881:Borates; D002712:Chlorides; D003486:Cyanides; D009942:Organometallic Compounds; D013440:Sulfides; D017973:Tungsten Compounds; D013455:Sulfur; D003300:Copper