[WS_(3)Cu_(2)]簇基超分子框的组装、结构及其三阶非线性光学响应  

[WS_(3)Cu_(2)] cluster-based supramolecular frame:Assembly,structure,and third-order nonlinear optical response

作　　者：余蕙敏 王志康 李洁[1] 宋瑛林 杜明浩 郎建平[1] YU Huimin;WANG Zhikang;LI Jie;SONG Yinglin;DU Minghao;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》2024年第1期71-78,共8页Chinese Journal of Inorganic Chemistry

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

摘　　要：将二(4-吡啶)硫烷(L_(1))、4,4'-二(4-吡啶)二苯甲酮(L_(2))分别与(Et_(4)N)(Tp*WS_(3))(A)(Tp*=三(3,5-二甲基吡唑)氢合硼酸根)和[Cu(Me CN)_(4)]PF_(6)进行反应,得到2个W/Cu/S簇基超分子化合物[Tp*WS_(3)Cu_(2)(L_(1))]_(2)(PF_(6))_(2)·2Me CN·2CHCl_(3)(1·2Me CN·2CHCl_(3))和[Tp*WS_(3)Cu_(2)(L_(2))(Me CN)]_(2)(PF_(6))_(2)·4Me CN (2·4Me CN)。对配合物1·2Me CN·2CHCl_(3)和2·4Me CN分别进行了单晶X射线衍射、核磁、质谱、红外、紫外可见和元素分析表征。单晶X射线衍射分析表明,它们是由2个L_(1)/L_(2)配体连接2个[Tp*WS_(3)Cu_(2)]~+簇核形成的阳离子型簇基超分子框。核磁氢谱和高分辨电喷雾离子化质谱(HRESI-MS)证明它们在溶液中具有一定的稳定性。并利用Z扫描技术测试了超分子化合物1·2Me CN·2CHCl_(3)和2·4MeCN溶液的三阶非线性光学特性,测试结果表明它们的三阶非线性光学响应强于前驱体A。Reactions of (Et_(4)N)(Tp*WS_(3))(A)(Tp*=hydridotris(3,5-dimethylpyrazol-1-yl)borate) and Cu(Ⅰ) salts[Cu(Me CN)_(4)]PF_(6)with di(pyridin-4-yl)sulfane (L_(1)) or bis(4-(pyridin-4-yl)phenyl)methanone (L_(2)) gave rise to two W/Cu/S cluster-based supramolecular compounds with the formula of[Tp*WS_(3)Cu_(2)(L_(1))]_(2)(PF_(6))_(2)·2MeCN·2CHCl_(3)(1·2MeCN·2CHCl_(3)) and[Tp*WS_(3)Cu_(2)(L_(2))(MeCN)]_(2)(PF_(6))_(2)·4MeCN (2·4MeCN),respectively.Both cluster-based supramolecular compounds were structurally characterized by single-crystal X-ray diffraction,~1H NMR,MS,IR,UV-Vis,and elemental analysis.Single crystal X-ray diffraction demonstrates that both compounds are cationic cluster-based supramolecule frames with similar butterfly-like cores.~1H NMR and high-resolution electrospray ionization mass spectrometry (HRESI-MS) demonstrated their stability in DMF solution.In addition,the Z-scan measurement reveals the third-order nonlinear optical responses of 1·2Me CN·2CHCl_(3) and 2·4Me CN were enhanced compared to that of their precursor A.CCDC:2257638,1·2Me CN·2CHCl_(3);2257639,2·4MeCN.

关 键 词：W/Cu/S簇 超分子框 三阶非线性光学性质 

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