化学
催化作用
硫茴香醚
光化学
单线态氧
活性氧
激进的
电子转移
活动站点
反应中间体
分子
立体化学
氧气
有机化学
生物化学
作者
Jiangpei Yuan,Zong‐Jie Guan,Hengyu Lin,Bing Yan,Kang‐Kai Liu,Hong‐Cai Zhou,Yu Fang
标识
DOI:10.1002/anie.202303896
摘要
Mimicking the active site and the substrate binding cavity of the enzyme to achieve specificity in catalytic reactions is an essential challenge. Herein, porous coordination cages (PCCs) with intrinsic cavities and tunable metal centers have proved the regulation of reactive oxygen species (ROS) generating pathways as evidenced by multiple photo-induced oxidations. Remarkably, in the presence of the Zn4 -μ4 -O center, PCC converted dioxygen molecules from triplet to singlet excitons, whereas the Ni4 -μ4 -O center promoted the efficient dissociation of electrons and holes to conduct electron transfer towards substrates. Accordingly, the distinct ROS generation behavior of PCC-6-Zn and PCC-6-Ni enables the conversion of O2 to 1 O2 and O2 ⋅- , respectively. In contrast, the Co4 -μ4 -O center combined the 1 O2 and O2 ⋅- together to generate carbonyl radicals, which in turn reacted with the oxygen molecules. Harnessing the three oxygen activation pathways, PCC-6-M (M=Zn/Ni/Co) display specific catalytic activities in thioanisole oxidation (PCC-6-Zn), benzylamine coupling (PCC-6-Ni), and aldehyde autoxidation (PCC-6-Co). This work not only provides fundamental insights into the regulation of ROS generation by a supramolecular catalyst but also demonstrates a rare example of achieving reaction specificity through mimicking natural enzymes by PCCs.
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