4.8 nm Concave {M<sub>72</sub>}(M=Co,Ni,Fe) metal-organic polyhedra capped by 18

本文刊于: 《Science China(Chemistry)》 2021年第0期

关键词:
clustercompounds thiacalix[4]arene gasse

Keywords:
cluster compounds,thiacalix[4]arene,gas separation,template synthesis,nanoparticles
摘要
     Three 4.8 nm isostructural{M72}(M=Co for CIAC-128,Ni for CIAC-129,Fe for CIAC-130) metal-organic polyhedra(MOPs) are constructed by eighteen M4-p-tert-butylthiacalix[4]arene (M4-TC4A) units bridged via sixteen four-connected 5,5′-(1H-1,2,4-triazole-3,5-diyl) diisophthalic acid (H4TADIPA) 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 C3H8 than CH4 under ambient conditions,and also exhibits separation selectivity for C2H6/CH4,C2H2/CH4,and C2H4/CH4.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).

基金项目:
supportedbytheNationalNaturalScienceFoundationofChina(21971233,21571172,51222404)

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