Stepwise addition of CuNCS onto [Et(4)N][Tp*WS(3)]: design, syntheses, structures and third-order nonlinear optical properties.
Stepwise reactions of [Et(4)N][Tp*WS(3)] () (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 1-4 equiv. of CuNCS (and Et(4)NBr in the case of three equiv. of CuNCS) afforded the [1 + 1] to [1 + 4] addition products [Et(4)N][Tp*WS(mu-S)(2)(CuNCS)].0.5CH(2)Cl(2) (.0.5CH(2)Cl(2)), [Et(4)N][Tp*W(mu(3)-S)(mu-S)(2)(CuNCS)(2)].ClCH(2)CH(2)Cl (.ClCH(2)CH(2)Cl), [Et(4)N](2)[Tp*W(mu(3)-S)(3)(CuNCS)(3)(mu(3)-Br)].1.5aniline (.1.5aniline), and {[Et(4)N][Tp*W(mu(3)-S)(3)(Cu-mu-SCN)(3)(Cu-mu(3)-NCS)]}(n) (). Compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, and single-crystal X-ray crystallography. The cluster anion of contains a [WS(2)Cu] core formed by addition of one CuNCS group onto the [Tp*WS(3)] species. The cluster anion of has a butterfly-shaped [WS(3)Cu(2)] core constructed by addition of two CuNCS groups onto the [Tp*WS(3)] species. The cluster dianion of consists of a cubane-like [Tp*WS(3)Cu(3)(mu(3)-Br)] core assembled by addition of three CuNCS groups onto the [Tp*WS(3)] species followed by filling a mu(3)-Br into the void of the incomplete cubane-like [Tp*WS(3)(CuNCS)(3)] fragment. has a 2D cluster-supported layer network in which each [Tp*WS(3)Cu(3)] core acting as a pyramidal 3-connecting node interconnects with the [Cu(NCS)(4)] units through thiocyanate bridges. In addition, the third-order nonlinear optical (NLO) performances of in DMF were also investigated by Z-scan techniques.
Wei
Zhen-Hong
ZH
College of Chemistry, Chemical Engineering and Materials Science, Suzhou University, Suzhou, 215123, P. R. China. jplang@suda.edu.cn.
Li
Hong-Xi
HX
Ren
Zhi-Gang
ZG
Lang
Jian-Ping
JP
Zhang
Yong
Y
Sun
Zhen-Rong
ZR
D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D017879:Isothiocyanates / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D055620:Optical Phenomena; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013057:Spectrum Analysis; D014414:Tungsten / Q000737:chemistry*
D017879:Isothiocyanates; D009942:Organometallic Compounds; D003300:Copper; D014414:Tungsten