title: Assembly of new Mo/Cu/S clusters from [Et4N][Tp*MoS(S4)] and Cu(I) salts: syntheses, structures and third-order nonlinear optical properties.
abstract: Reactions of [Et4N][Tp*MoS(S)4] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) with 3 equiv. of CuX (X = Cl, Br, I, CN) or [Cu(MeCN)4]ClO4 in CH2Cl2-MeCN or CH2Cl2-DMF afforded [Et4N]2[Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] (2), [Et4N][Tp*Mo(μ3-S)3(CuX)3] (3: X = Br; 4: X = I), [Et4N][Tp*MoO(μ-S)2(CuX)] (5: X = I; 6: X = CN) and [Tp*Mo(μ3-S)3Cu3(μ3-S')]4 (7). Compounds 2-7 were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, electrospray ion mass spectra (ESI-MS) and X-ray crystallography. The cluster dianion of 2 has a complete cubane-like [Tp*Mo(μ3-S)3(CuCl)3(μ3-Cl)] structure while the anion of 3 or 4 consists of an incomplete cubane-like [Tp*Mo(μ3-S)3(CuX)3] structure. The anion of 5 or 6 has a binuclear structure, in which one [Tp*MoO(μ-S)2] moiety and one CuX unit are linked by a pair of μ-S atoms. The structure of 7 may be considered as a supercube whose eight corners are occupied by four incomplete cubane-like [Tp*Mo(μ3-S)3Cu3] fragments and four μ3-S' atoms. The third-order nonlinear optical (NLO) properties of 2-6 in DMF were investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80 fs pulse width at 800 nm. Compounds 2-6 exhibited good NLO performances and their NLO responses were enhanced relative to that of 1.
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
authors.forename: Zhi-Yuan
authors.initials: ZY
authors.lastname: Zhang
authors.forename: Wei-Jie
authors.initials: WJ
authors.lastname: Gong
authors.forename: Fan
authors.initials: F
authors.lastname: Wang
authors.forename: Min-Min
authors.initials: MM
authors.lastname: Chen
authors.forename: Li-Kuan
authors.initials: LK
authors.lastname: Zhou
authors.forename: Zhi-Gang
authors.initials: ZG
authors.lastname: Ren
authors.forename: Zhen-Rong
authors.initials: ZR
authors.lastname: Sun
authors.forename: Jian-Ping
authors.initials: JP
authors.lastname: Lang
mesh_terms: D003300:Copper / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D055620:Optical Phenomena; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012492:Salts / Q000138:chemical synthesis / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D012492:Salts; D013455:Sulfur; D003300:Copper; D008982:Molybdenum