Designed assembly of heterometallic cluster organic frameworks based on Th_6 cluster  

作　　者：Xianghe Kong Xiaoli Liao Zhenkun Huang Lei Mei Hongqing Wang Kongqiu Hu Weiqun Shi 

机构地区：[1]School of Chemistry and Chemical Engineering,University of South China,Hengyang 421001,China [2]Laboratory of Nuclear Energy Chemistry,Institute of High Energy Physics,Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Chinese Chemical Letters》2024年第11期329-333,共5页中国化学快报（英文版）

基　　金：support of the National Natural Science Foundation of China(Nos.22076187,22122609);the Hunan Province Natural Science Foundation of China(No.2023JJ40530);the Scientific Research Fund of Hunan Provincial Education Department(No.22C0202);The National Science Fund for Distinguished Young Scholars(No.21925603)。

摘　　要：Four novel compounds based on hexanuclear thorium cluster were synthesized and characterized.Compound 1[Th_(6)(HPy C)_(8)(HCOO)_(4)]is formed by replacing formate ligands of preassembled thorium cluster[Th_(6)O_(4)(OH)_(4)(H_(2)O)_(6)(HCOO)_(12)]with eight H_(2)Py C(4-pyrazolecarboxylic acid)under solvothermal conditions.Each of the HPy C^(-)ligands is coordinated with one Cu^(2+)to form the(4,8)-connected scu-net structure of compound 2[(Cu Cl_(2))_(2)Th_(6)(HPy C)_8(HCOO)_(4)].In compound 3[(Cu Cl_(2))_(2)Th_(6)(HPy C)_(10)(HCOO)_(4)],ten of the formate ligands of preassembled Th_(6)cluster are replaced by HPy C^(-)ligands.Compared with compound 2,the two extra HPy C^(-)ligands in the equatorial plane of the Th_(6)cluster in compound 3 are not further connected to copper ions.Therefore,the topology structure of compound 3 is same with that of compound 2.Compound 4[(Cu_(3)Cl_(2))(Cu Cl_(2))Th_(6)(Py C)_(3)(HPy C)_(4)(HCOO)_(5)]contains three kinds of metal nodes,Th_(6)cluster,Cu_(3)cluster and mononuclear Cu^(2+),and exhibits a novel(5,7)-connected net structure,which was first discovered in actinide MOFs.Furthermore,considering the satisfactory stability of compound 4 and its unsaturated metal nodes and Lewis acid sites,the catalysis of cycloaddition of CO_(2)was further studied.We found that this thorium-copper heterometallic cluster organic framework can be used as a potential actinide functional material for catalyzing the efficient CO_(2)conversion to value-added products.

关 键 词：Actinide Hexanuclear thorium cluster Heterometallic organic frameworks Coordination chemistry Catalytic cycloaddition 

分 类 号：O641.4[理学—物理化学]