Diverse Tp-Capped W-Cu-S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines
Diverse Tp-Capped W-Cu-S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines
复制标题
涉及膦原位硫醇化的一锅法组装得到多种 Tp 封端的 W-Cu-S 团簇
DOI：
10.1021/acs.inorgchem.5b02765
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发表时间：
2016
影响因子：
4.6
通讯作者：
Jian-Ping Lang
中科院分区：
文献类型：
--
作者：
Xin Zhao;Feng Zhou;Quan Liu;Qiu-Fang Chen;Jun-Yi Yang;Wen-Hua Zhang;Ying-Lin Song;Jian-Ping Lang
在不存在/存在S8的情况下，[Et 4 N][Tp* WS 3] [1; Tp* =三聚氰胺（3，5-二甲基吡唑-1-基）硼酸酯]与[Cu（MeCN）4] PF 6和双-或四膦配体1，2-双1，3-双（二苯基膦基）乙烷（dppe）1，4-双（二苯基膦基）丙烷（dppp）（二苯基膦基）丁烷（dppb）和N，N，N′，N′-四（二苯基膦甲基）乙二胺（dppeda）产生六个W-Cu-S簇，即，[（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）和[（Tp*WS3Cu3）2（Ph2PS2）3（μ6-Cl）0.5]（PF 6）0.5·0.75CH2Cl2（7·0.75CH2Cl2）。化合物2 - 7通过元素分析、IR、UV-vis、~ 1H和~（31）P {1H} NMR、电喷雾电离质谱和X射线晶体学进行了表征。对于2，dppe配体桥接一对蝴蝶形[Tp* WS 3Cu 2]核，形成双蝴蝶形结构。对于4，dppp配体是敏感的S协会，并形成原位生成的dpppS 2配体，支持八核双半开立方烷结构和对比类似的系统，其中形成了一个五核摩托车形的阳离子簇3与S8的情况下。一个较长的dppb配体很容易在5和6中转化为S基配体，随后在一对蝴蝶形（5）和巢形（6）簇之间充当桥梁。进一步使用四膦配体dppeda在簇形成中，在S8的存在下，导致意外的配体降解，得到[Ph 2 PS2]−阴离子。三个[Ph 2 PS2]−阴离子并置一对巢状的簇核，产生一个八核簇，7，具有一个笼状结构来包裹μ6-Cl-。用Z扫描技术研究了2 - 7在N，N-二甲基甲酰胺中的三阶非线性光学性质，发现2 - 6有反饱和吸收，而7有明显的饱和吸收。2 - 7均表现出自聚焦效应，其超极化率γ值在4.71 × 10-30-1.02 × 10- 29 esu之间，比1提高了440-1000倍。通过膦配体的原位巯基化反应，从1生成4 - 7，为W-Cu-S簇合物的设计和组装提供了一条新的途径，具有有趣的结构阵列和更好的非线性光学性能。
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]PF6and bis- or tetraphosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), andN,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). Compounds2–7are characterized by elemental analysis, IR, UV–vis,1H and31P{1H} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For2, the dppe ligand bridges a pair of butterfly-shaped [Tp*WS3Cu2] cores to form a double-butterfly-shaped structure. For4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS2ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster3is formed with the absence of S8. A longer dppb ligand readily converts to S-based ligands in5and6, 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 of2–7inN,N-dimethylformamide, investigated using aZ-scan technique at 532 nm, show that2–6have a reverse saturable absorption, while7has a notable saturable absorption. All of2–7exhibit a self-focusing effect with hyperpolarizability γ values in the range of 4.71 × 10–30–1.02 × 10–29esu, which are 440–1000 times higher than that of1. The formation of4–7from1through 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.