Selective Photooxidation of Amines and Sulfides Triggered by a Superoxide Radical Using a Novel Visible-Light-Responsive Metal–Organic Framework

Photocatalysis is
an efficient and sustainable approach to convert solar energy into
chemical energy, simultaneously supplying valuable chemicals. In this
study, a novel metal–organic framework (MOF) compound is constructed
from anthracene-based organic linkers, which shows visible-light absorption
and efficient photoinduced charge generation property. It was applied
for triggering photooxidation of benzylamines and sulfides in the
presence of environmental benign
oxidants of molecular oxygen or hydrogen peroxide. Results show that
it is a highly selective photocatalyst for oxidation reactions to
produce valuable imines or sulfoxides. We further investigate the
underlying mechanism for these photocatalytic reactions by recognizing
reactive oxygen species in the reactions. It has been demonstrated
that the superoxide radical (O2•–), generated by electron transfer from a photoexcited MOF to oxidants,
serves as the main active species for the oxidations. The work demonstrates
the great potential of photoactive MOFs for the transformation of
organic chemicals into valuable complexes.