Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 49, Pages 20763-20771Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c09727
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Funding
- NSFC [21725101, 21673213, 21521001]
- Supercomputing Center of University of Science and Technology of China
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Excitonic effects caused by Coulomb interactions between electrons and holes play subtle and significant roles on photocatalysis, yet have been long ignored. Herein, porphyrinic covalent organic frameworks (COFs, specifically DhaTph-M), in the absence or presence of different metals in porphyrin centers, have been shown as ideal models to regulate excitonic effects. Remarkably, the incorporation of Zn2+' in the COF facilitates the conversion of singlet to triplet excitons, whereas the Ni2+ introduction promotes the dissociation of excitons to hot carriers under photoexcitation. Accordingly, the discriminative excitonic behavior of DhaTph-Zn and DhaTph-Ni enables the activation of O-2 to O-1(2) and O-2(center dot-), respectively, under visible light irradiation, resulting in distinctly different activity and selectivity in photocatalytic terpinene oxidation. Benefiting from these results, DhaTph-Ni exhibits excellent photocatalytic activity in O-2(center dot-)-engaged hydroxylation of boronic acid, while DhaTph-Zn possesses superior performance in O-1(2)-mediated selective oxidation of organic sulfides. This work provides indepth insights into molecular oxygen activation and opens an avenue to the regulation of excitonic effects based on COFs.
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