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Ambient Chemical Fixation of CO 2 Using a Robust Ag 27 Cluster‐Based Two‐Dimensional Metal–Organic Framework
Author(s) -
Zhao Meihua,
Huang Shan,
Fu Qiang,
Li Weifeng,
Guo Rui,
Yao Qingxia,
Wang Fenglong,
Cui Ping,
Tung ChenHo,
Sun Di
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202007122
Subject(s) - porphyrin , density functional theory , catalysis , cationic polymerization , metal organic framework , cluster (spacecraft) , chemistry , alkyne , substrate (aquarium) , photochemistry , lewis acids and bases , steric effects , transition metal , metal , materials science , polymer chemistry , computational chemistry , organic chemistry , adsorption , oceanography , computer science , programming language , geology
Abstract Unprecedented double S 2− templated Ag 27 clusters have been stabilized by 5,10,15,20‐tetra(4‐pyridyl)porphyrin (TPyP‐H 2 ) ligands to afford a robust 2D metal–organic framework ( Ag27‐MOF ). This silver cluster‐assembled material serves as a highly efficient heterogeneous catalyst for the cyclization of both terminal and internal propargylamines with CO 2 under atmospheric pressure. Density functional theory (DFT) calculations illustrate that the high catalytic activity and broad substrate scope are attributable to the saddle‐shaped metallic node in Ag27‐MOF , which features an accessible platform with high‐density silver atoms as π‐Lewis acid sites for activating C≡C triple bonds. As a result, different sterically hindered alkyne substrates can be effectively activated through π‐interactions with these cationic silver centers.