W/Cu/S簇基超分子大环及其三阶非线性光学性质  

W/Cu/S cluster⁃based supramolecular macrocycles and their third⁃order nonlinear optical responses

作　　者：黄志文 刘琦 郎建平[1] HUANG Zhiwen;LIU Qi;LANG Jianping(Suzhou Key Laboratory of Precision Transformation of Resource Molecules,College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou,Jiangsu 215123,China)

机构地区：[1]苏州大学材料与化学化工学部,苏州市资源分子精准转化重点实验室,苏州215123

出　　处：《无机化学学报》2025年第1期79-87,共9页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.22301204,21773163);苏州市资源分子精准转化重点实验室(No.SZS201905)资助。

摘　　要：以前驱簇[Et_(4)N][Tp*WS_(3)(CuCl)_(3)]与三氟甲烷磺酸银(AgOTf)及3个有机桥联配体2,5‑二(吡啶‑4‑基)噻吩(L1)、5,5'‑双(4‑吡啶基)‑2,2'‑双噻吩(L_(2))和2,7‑双(4‑吡啶基)芘(L_(3))分别反应,得到了3个阳离子型W/Cu/S簇基超分子大环化合物[(Tp*WS_(3)Cu_(3))_(2)(μ‑Cl)_(2)(μ_(4)‑Cl)(L_(1))]_(2)(OTf)_(2)(1)、[(Tp*WS_(3)Cu_(3))_(2)(μ‑Cl)_(2)(μ_(4)‑Cl)(L_(2))]_(2)(OTf)_(2)·2CHCl_(3)(2·2CHCl_(3))和[(Tp*WS_(3)Cu_(3))_(2)(μ‑Cl)_(2)(μ_(4)‑Cl)(L_(3))]_(2)(OTf)_(2)·2DMF(3·2DMF),其中Tp*=hydridotris(3,5‑dimethylpyrazol‑1‑yl)borate。对3个化合物分别进行了单晶X射线衍射、核磁、质谱、红外光谱、紫外可见光谱和元素分析等结构表征。单晶X射线衍射结果表明,3个大环的主体均是由2个L1、L_(2)和L_(3)配体和3个氯桥连接的[(Tp*WS_(3)Cu_(3))_(2)(μ‑Cl)_(2)(μ_(4)‑Cl)]^(2+)阳离子簇核组成。3个大环通过不同方式堆叠形成三维结构。核磁氢谱(^(1)H NMR)和电喷雾飞行质谱(ESI‑TOF MS)结果表明这些化合物在溶液中有较好的稳定性。Z扫描测试结果表明,3个化合物的溶液有一定的三阶非线性光学响应。The precursor cluster[Et4N][Tp*WS_(3)(CuCl)_(3)]was treated with silver trifluoromethane sulfonate(AgOTf),followed by the assembly with three bridging ligands 2,5‑di(pyridin‑4‑yl)thiophene(L1),5,5'‑bis(4‑pyridinyl)‑2,2'‑bithiophene(L_(2)),and 2,7‑di(4‑pyridinyl)pyrene(L_(3)),resulting in three cationic W/Cu/S cluster‑based supramolecular macrocycles[(Tp*WS_(3)Cu_(3))_(2)(μ‑Cl)_(2)(μ_(4)‑Cl)(L_(1))]_(2)(OTf)_(2)(1),[(Tp*WS_(3)Cu3)(μ‑Cl)_(2)(μ_(4)‑Cl)(L_(2))]_(2)(OTf)_(2)·2CHCl_(3)(2·2CHCl_(3)),and[(Tp*WS_(3)Cu3)(μ‑Cl)_(2)(μ_(4)‑Cl)(L_(3))]_(2)(OTf)_(2)·2DMF(3·2DMF),respectively.Structural characterizations including single‑crystal X‑ray diffraction,NMR spectroscopy,mass spectrometry,IR spectroscopy,UV‑Vis spectroscopy,and elemental analysis were carried out for these compounds.X‑ray analysis revealed that the main backbones of the three macrocycles are composed of a pair of L1,L_(2),or L_(3)ligands and three chlorine‑bridged[(Tp*WS_(3)Cu_(3))_(2)(μ‑Cl)_(2)(μ_(4)‑Cl)]^(2+)cationic cluster cores.And they form 3D structures by stacking in different ways.The^(1)H NMR and electrospray ionization time‑of‑flight mass spectrometry(ESI‑TOF MS)results indicated their good stability in solution.These three compounds exhibited enhanced third‑order nonlinear optical properties in DMF compared to the precursor[Et4N][Tp*WS_(3)(CuCl)_(3)].CCDC:2354373,1;2354374,2·2CHCl_(3);2354375,3·2DMF.

关 键 词：W/Cu/S簇 组装 超分子大环 结构 三阶非线性光学响应 

分 类 号：O614.121[理学—无机化学] O614.613[理学—化学]