4.8 nm Concave {M_(72)}(M=Co,Ni,Fe) metal-organic polyhedra capped by 18 calixarenes  

作　　者：Haitao Han Liang Kan Ping Li Guoshuai Zhang Kaiyue Li Wuping Liao Yunling Liu Wei Chen Chunhua T.Hu 

机构地区：[1]State Key Laboratory of Rare Earth Resource Utilization,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China [2]State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,College of Chemistry,Jilin University,Changchun 130012,China [3]State Key Laboratory of Electroanalytical Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China [4]Department of Chemistry,New York University,100 Washington Square East,Room 1001,New York,NY 10003,USA [5]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Science China Chemistry》2021年第3期426-431,共6页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21971233,21571172,51222404)。

摘　　要：Three 4.8 nm isostructural{M_(72)}(M=Co^(Ⅱ) for CIAC-128,Ni^(Ⅱ) for CIAC-129,Fe^(Ⅱ) for CIAC-130) metal-organic polyhedra(MOPs) are constructed by eighteen M_(4)-p-tert-butylthiacalix[4]arene (M_(4)-TC4A) units bridged via sixteen four-connected 5,5′-(1H-1,2,4-triazole-3,5-diyl) diisophthalic acid (H_(4)TADIPA) linkers.These MOPs are featured with a rarely reported concave coordination cage,which can be simplified as a squeezed double-decker hexagonal prism pressed from the top and bottom hexagonal faces.Furthermore,CIAC-128,CIAC-129 and CIAC-130 are the highest nuclearity discrete clusters of Co,Ni and Fe reported so far.CIAC-128 has higher separation selectivity of C_(3)H_(8) than CH_(4) under ambient conditions,and also exhibits separation selectivity for C_(2)H_(6)/CH_(4),C_(2)H_(2)/CH_(4),and C_(2)H_(4)/CH_(4).In addition,CIAC-128 can provide the cavity for the confined synthesis of noble metal nanoclusters such as Pd nanoclusters and the resulting Pd@CIAC-128 hybrids show higher electrocatalytic activity than commercial Pt/C towards hydrogen evolution reaction (HER).

关 键 词：cluster compounds arene gas separation template synthesis nanoparticles 

分 类 号：O641.4[理学—物理化学] TB383.1[理学—化学]