title: Diverse Tp*-Capped W-Cu-S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines.
abstract: In the absence/presence of S8, the one-pot assembly of [Et4N][Tp*WS3] [1; Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] with [Cu(MeCN)4]PF6 and bis- or tetraphosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), and N,N,N',N'-tetrakis(diphenylphosphinomethyl)ethylenediamine (dppeda) produces six W-Cu-S clusters, namely, [(Tp*WS3Cu2Cl)2(dppe)] (2), [Tp*WS3Cu4(dppp)2(μ4-Cl)(μ-Cl)]PF6·MeCN (3·MeCN), [(Tp*WS3Cu3)2(μ4-Cl)(μ-Cl)2(dpppS2)] (4), [(Tp*WS3Cu2Cl)2(dppbS2)]·2MeCN·2H2O (5·2MeCN·2H2O), [(Tp*WS3Cu3Cl2)2(dppbS2)] (6), and [(Tp*WS3Cu3)2(Ph2PS2)3(μ6-Cl)0.5](PF6)0.5·0.75CH2Cl2 (7·0.75CH2Cl2). Compounds 2-7 are characterized by elemental analysis, IR, UV-vis, (1)H and (31)P{(1)H} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For 2, the dppe ligand bridges a pair of butterfly-shaped [Tp*WS3Cu2] cores to form a double-butterfly-shaped structure. For 4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS2 ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster 3 is formed with the absence of S8. A longer dppb ligand readily converts to S-based ligands in 5 and 6, subsequently serving as bridges between a pair of a butterfly-shaped (5) and nest-shaped (6) clusters. Further use of a tetraphosphine ligand, dppeda, in the cluster formation, with the presence of S8, leads to an unexpected ligand degradation to give the [Ph2PS2](-) anions. Three [Ph2PS2](-) anions juxtapose a pair of nest-shaped cluster cores to yield an octanuclear cluster, 7, featuring a cage to encapsulate μ6-Cl(-). The third-order nonlinear-optical (NLO) properties of 2-7 in N,N-dimethylformamide, investigated using a Z-scan technique at 532 nm, show that 2-6 have a reverse saturable absorption, while 7 has a notable saturable absorption. All of 2-7 exhibit a self-focusing effect with hyperpolarizability γ values in the range of 4.71 × 10(-30)-1.02 × 10(-29) esu, which are 440-1000 times higher than that of 1. The formation of 4-7 from 1 through the in situ thiolation of phosphine ligands presents a new approach to the design and assembly of the W-Cu-S clusters with interesting structural arrays and better NLO properties.
authors.affiliation: State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, Jiangsu, P. R. China.|State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , Shanghai 200032, P. R. China.
authors.forename: Xin
authors.initials: X
authors.lastname: Zhao
authors.affiliation: School of Physical Science and Technology, Soochow University , Suzhou 215006, Jiangsu, P. R. China.
authors.forename: Feng
authors.initials: F
authors.lastname: Zhou
authors.affiliation: State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, Jiangsu, P. R. China.
authors.forename: Quan
authors.initials: Q
authors.lastname: Liu
authors.affiliation: State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, Jiangsu, P. R. China.
authors.forename: Qiu-Fang
authors.initials: QF
authors.lastname: Chen
authors.affiliation: School of Physical Science and Technology, Soochow University , Suzhou 215006, Jiangsu, P. R. China.
authors.forename: Jun-Yi
authors.initials: JY
authors.lastname: Yang
authors.affiliation: State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, Jiangsu, P. R. China.
authors.forename: Wen-Hua
authors.initials: WH
authors.lastname: Zhang
authors.affiliation: School of Physical Science and Technology, Soochow University , Suzhou 215006, Jiangsu, P. R. China.
authors.forename: Ying-Lin
authors.initials: YL
authors.lastname: Song
authors.affiliation: State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, Jiangsu, P. R. China.|State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , Shanghai 200032, P. R. China.
authors.forename: Jian-Ping
authors.initials: JP
authors.lastname: Lang