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Design of a Polyoxometalate-Based Metal–Organic Framework for Photocatalytic C(sp3)–H Oxidation of Toluene
journal contribution
posted on 2022-01-25, 14:05 authored by Jiachen Jiao, Xiaomei Yan, Songzhu Xing, Ting Zhang, Qiuxia HanA powerful and promising route for
developing novel photocatalysts
for light-driven toluene oxidation in water under mild conditions
is presented. Herein, a novel polyoxometalate-based metal–organic
framework (POMOF), {Co4W22-DPNDI}, is prepared
by incorporating the unusual Co4-sandwiched POM anion [Co4(μ-OH)2(SiW11O39)2]10– ({Co4W22}) and
the photoactive organic bridging link N,N′-bis(4-pyridylmethyl)naphthalene diimide (DPNDI) into a framework. {Co4W22} is a good candidate for photocatalytic water
oxidation. DPNDI is easily excited to form the radical species DPNDI*
in the presence of an electron donor, which is beneficial for activation
of the inert O2. Anion···π interactions
and covalent bonds between {Co4W22} and DPNDI
facilitate electron–hole separation and electron transfer. {Co4W22-DPNDI} displays high catalytic activity for the
activation of the C(sp3)–H bond of toluene using
light as a driving force and inexpensive water as an oxygen source
under mild conditions. In particular, the yield and selectivity are
improved by replacing oxygen with water, which may be ascribed to
the release of protons during the water oxidation process that facilitate
the generation of •OH.
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developing novel photocatalysts10 – supdriven toluene oxidationwater oxidation processsup >• supradical species dpndi11 subphotocatalytic water oxidationc ( sptoluene using lightoh )< subphotocatalytic cn inexpensive waterreplacing oxygenpromising routepomof ),oxygen sourcenovel polyoxometalatemild conditionsgood candidateelectron transferelectron donoreasily exciteddriving forcecovalent bonds