Metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)represent two dominant kinds of reticular materials.Mutual chemical conversion of these two species,however,still remains unreported.Herein,the reacti...Metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)represent two dominant kinds of reticular materials.Mutual chemical conversion of these two species,however,still remains unreported.Herein,the reaction of a two-dimensional MOF,Ni_(3)(HITP)_(2)(HITP=2,3,6,7,10,11-hexaiminotriphenylene),with 1,1,3,3-tetramethoxypropane induces the cyclization transformation of partial bis(diimine)nickel coordination subunits to tetraaza[14]annulene(TAA)metallomacrocycle moieties.A hemi-covalent organic framework,P-Ni_(3)(TAA)_(3),with different conversion efficiencies(P)of 34-72%for bis(diimine)nickel units depending on the reaction time has been obtained and preserves permanent porosity and crystallinity.The corresponding time-dependent conversion has been assessed by FT-IR spectroscopy,XPS,SEM,TEM,and powder X-ray diffraction analyses.In comparison with Ni_(3)(HITP)_(2),40%-Ni_(3)(TAA)_(3) exhibits improved chemical stability under acidic conditions and significantly enhanced catalytic properties towards the photocatalytic CO_(2) reduction.This result will be surely helpful in mutual investigations covering both MOFs and COFs.展开更多
基金support from the Natural Science Foundation of China(No.22175020,22131005,22072004,21631003)the Fundamental Research Funds for the Central Universities(No.FRF-BD-20-14A)University of Science and Technology Beijing is gratefully acknowledged.
文摘Metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)represent two dominant kinds of reticular materials.Mutual chemical conversion of these two species,however,still remains unreported.Herein,the reaction of a two-dimensional MOF,Ni_(3)(HITP)_(2)(HITP=2,3,6,7,10,11-hexaiminotriphenylene),with 1,1,3,3-tetramethoxypropane induces the cyclization transformation of partial bis(diimine)nickel coordination subunits to tetraaza[14]annulene(TAA)metallomacrocycle moieties.A hemi-covalent organic framework,P-Ni_(3)(TAA)_(3),with different conversion efficiencies(P)of 34-72%for bis(diimine)nickel units depending on the reaction time has been obtained and preserves permanent porosity and crystallinity.The corresponding time-dependent conversion has been assessed by FT-IR spectroscopy,XPS,SEM,TEM,and powder X-ray diffraction analyses.In comparison with Ni_(3)(HITP)_(2),40%-Ni_(3)(TAA)_(3) exhibits improved chemical stability under acidic conditions and significantly enhanced catalytic properties towards the photocatalytic CO_(2) reduction.This result will be surely helpful in mutual investigations covering both MOFs and COFs.
