Diverse Tp*-Capped W–Cu–S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

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• 作者：Xin Zhao ; Feng Zhou ; Quan Liu ; Qiu-Fang Chen ; Jun-Yi Yang ; Wen-Hua Zhang ; Ying-Lin Song ; Jian-Ping Lang
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：February 15, 2016
• 年：2016
• 卷：55
• 期：4
• 页码：1861-1871
• 全文大小：598K
• ISSN：1520-510X

文摘

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, ¹H and ³¹P{¹H} 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.