Issue 12, 2018

Direct evidence of charge separation in a metal–organic framework: efficient and selective photocatalytic oxidative coupling of amines via charge and energy transfer

Abstract

The selective aerobic oxidative coupling of amines under mild conditions is an important laboratory and commercial procedure yet a great challenge. In this work, a porphyrinic metal–organic framework, PCN-222, was employed to catalyze the reaction. Upon visible light irradiation, the semiconductor-like behavior of PCN-222 initiates charge separation, evidently generating oxygen-centered active sites in Zr-oxo clusters indicated by enhanced porphyrin π-cation radical signals. The photogenerated electrons and holes further activate oxygen and amines, respectively, to give the corresponding redox products, both of which have been detected for the first time. The porphyrin motifs generate singlet oxygen based on energy transfer to further promote the reaction. As a result, PCN-222 exhibits excellent photocatalytic activity, selectivity and recyclability, far superior to its organic counterpart, for the reaction under ambient conditions via combined energy and charge transfer.

Graphical abstract: Direct evidence of charge separation in a metal–organic framework: efficient and selective photocatalytic oxidative coupling of amines via charge and energy transfer

Supplementary files

Article information

Article type
Edge Article
Submitted
14 Dec 2017
Accepted
19 Feb 2018
First published
20 Feb 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 3152-3158

Direct evidence of charge separation in a metal–organic framework: efficient and selective photocatalytic oxidative coupling of amines via charge and energy transfer

C. Xu, H. Liu, D. Li, J. Su and H. Jiang, Chem. Sci., 2018, 9, 3152 DOI: 10.1039/C7SC05296K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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