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Catalysis Science & Technology
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Journal Name
ARTICLE
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By judicious selection of the imidazole linker, we have
demonstrated that the photocatalytic efficacy of
heterogeneous solids can be tuned to create an improved
photocatalyst in a demanding C–H activation reaction, utilizing
visible light (λ > 515 nm). Through a combination of UV/Vis, XAS
spectroscopy and theoretical simulations, we have shown that
the reduction step and the range of light adsorbed to activate
the cobalt site play a pivotal role in this reaction. This can be
controlled and enhanced through astute selection of the
imidazole linker, with benzimidazole (ZIF-9) preventing the
LMCT seen with 2-methylimidazole (ZIF-67), leading to ZIF-9
being a superior photocatalyst. These findings open up
possibilities for a wider range of functionalized imidazole linkers
to be experimentally and computationally screened for this
reaction, towards developing an optimized photocatalytic
species. Controlling the precise coordination environment of
the cobalt species in the ZIF-9 framework, confers the benefits
of a stable, recyclable heterogeneous photocatalyst for
effecting sustainable organic transformations.
Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
The work was funded by the EU’s Horizon 2020 program under
grant number 720783 (MULTI2HYCAT) and EPSRC (UK)
(EP/N013883/1). CPR was funded through a joint University of
Southampton and A*STAR, Singapore scholarship. The
beamtime was carried out at B18, Diamond Light Source under
proposal SP-15151 via the UK Catalysis Hub Beamtime
Allocation Group.
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