Metal-modulated copper phenylacetylide synchronously enhances electron-proton transfer for high-efficiency...

The d-π interaction plays a pivotal role in the photocatalytic performance of metal-organic coordination polymers, acting as a key mechanism and driving force for enhancing the separation and transport of photogenerated charge carriers. Herein, copper phenylacetylide (PACu₄) was employed as a model system, and a series of PACu₃X₁ (X = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn) photocatalysts were synthesized by incorporating additional 3d transition metals. Among them, PACu₃Mn₁ exhibited exceptional photocatalytic activity and stability in the oxidation of triphenylphosphine and anthracene. Experiments combined with theoretical calculations confirmed that the MnCu heterometallic center enhances the d-π polarization effect, improving the photogenerated charges separation. Furthermore, in photocatalytic aerobic reactions, the newly formed MnO sites functioned as high-speed proton hopping transport channels, continuously promoting electron transport and thereby significantly boosting the formation of ∙O₂^- via electron transfer pathways. This design strategy, leveraging metal-regulated synergistic enhancement of electron and proton transport, opens up new avenues for developing highly efficient metal-organic coordination polymer photocatalysts.