We synthesized two new MOFs (Cu-Tpxa-1 and Cu-Tpxa-2) that were used as heterogeneous photocatalysts, combining photocatalysis and copper catalysis to achieve the decarboxylative radical cyanation reactions. The new heterogeneous catalysis...

Cuprous clusters are well known for their important fluorescent properties and tunable redox behavior, but the coordinated protecting groups restrict their application in photocatalysis, in particular, the inner-sphere activation of substrates. By modifying fluorescent cuprous clusters with terminal iodides into two-dimensional coordination sheets, we report a photocatalytic regulator to synergistically combine electron transfer and energy transfer for the oxidative coupling of benzoquinone and terminal alkynes. Under visible light irradiation, the well-modified excited state of the cuprous clusters in the coordination sheets reduces benzoquinones to generate aoxy radicals through electron transfer and activates oxygen through energy transfer. The aoxy radicals interact with copper-coordinated phenylacetylene to form an active intermediate, which is further oxidized by the in situ formed active oxygen species and aryl ketones are obtained. The warranted potential of the excited coordination sheets enables the reductive activation of thianthrenium salts as radical precursors, facilitating radical capture and further C−N coupling via an inner-sphere activation mechanism. The new catalytic approach optimizes the redox properties and excited-state lifetime, shortens the electron transfer steps, and promotes the potential collision of a low concentration of active species in tandem catalytic cycles, thus paving a new way to develop ecologically benign, cost-effective, multipurpose, and flexible catalytic systems.