A Stable Triphenylamine-Based Zn(II)-MOF for Photocatalytic H₂ Evolution and Photooxidative Carbon-Carbon Coupling Reaction

Efficient charge transfer has always been a challenge in heterogeneous MOF-based photoredox catalysis due to the poor electrical conductivity of the MOF photocatalyst, the toilless electron-hole recombination, and the uncontrollable host-guest interactions. Herein, a propeller-like tris(3'-carboxybiphenyl)amine (H) ligand was synthesized to fabricate a 3D Zn₃O cluster-based Zn(II)-MOF photocatalyst, Zn₃(TCBA)₂(μ-H₂O)H₂O (Zn-TCBA), which was applied to efficient photoreductive H₂ evolution and photooxidative aerobic cross-dehydrogenation coupling reactions of N-aryl-tetrahydroisoquinolines and nitromethane. In Zn-TCBA, the ingenious introduction of the meta-position benzene carboxylates on the triphenylamine motif not only promotes Zn-TCBA to exhibit a broad visible-light absorption with a maximum absorption edge of 480 nm but also causes special phenyl plane twists with dihedral angles of 27.8-45.8° through the coordination to Zn nodes. The semiconductor-like Zn clusters and the twisted TCBA antenna with multidimensional π interaction sites facilitate photoinduced electron transfer to render Zn-TCBA a good photocatalytic H₂ evolution efficiency of 27.104 mmol·g^-1·h^-1 in the presence of [Co(bpy)₃]Cl₂ under visible-light illumination, surpassing many non-noble-metal MOF systems. Moreover, the positive enough excited-state potential of 2.03 V and the semiconductor-like characteristics of Zn-TCBA endow Zn-TCBA with double oxygen activation ability for photocatalytic oxidation of N-aryl-tetrahydroisoquinoline substrates with a yield up to 98.7% over 6 h. The durability of Zn-TCBA and the possible catalytic mechanisms were also investigated by a series of experiments including PXRD, IR, EPR, and fluorescence analyses.