Anthraquinone-Based Metal-Organic Frameworks as a Bifunctional Photocatalyst for C-H Activation

Metal-organic frameworks (MOFs) have gained attention as multifunctional catalytic platforms, allowing us to gain important insights into synergistically activating both C-H bonds and oxygen for improving oxidation. Herein, by ingenious incorporation of anthraquinone, we report an anthraquinone-based MOF as a bifunctional heterogeneous photocatalytic platform to simultaneously activate inert C(sp³)-H bonds and oxygen for C-H bond oxidation. Making use of the rigid framework with the fixation and isolation effect, both a great chemical stability and bifunctional synergistic photocatalytic effects were obtained through the immobilization of anthraquinone into a MOF. Importantly, while decorating two carboxyl groups on anthraquinone, the carbonyl groups of anthraquinone photosensitizers were not involved in coordinating the self-assembly and orderly arranged on the wall of channels that were constructed through a π-π interaction between the anthraquinone moieties in the adjacent layers, which was beneficial to form and stabilize the excited-state radical intermediates in the molecule-fenced channels, and the close proximity between the catalytic sites and the substrates to abstract a hydrogen atom from the substrate through the hydrogen atom transfer process aimed at activating the inertness of C-H bonds. Moreover, high-density-distributed anthraquinone dyes in the confined channels would activate oxygen to form singlet oxygen (¹O₂) through an energy transfer pathway, further promoting inert C(sp³)-H bond oxidation efficiency. Under visible light irradiation, this anthraquinone-based MOF was successfully applied to explore activation and oxidation of a series of substrates containing benzylic C(sp³)-H bonds in the presence of air or oxygen to produce the corresponding carbonyl products. This bifunctional photocatalytic platform based on a heterogeneous MOF provides an available catalytic avenue to develop a scalable and sustainable synthetic strategy using green and sustainable oxygen as the potent oxidant.