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

Inorg Chem

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an, Shaanxi 710127, China.

Published: May 2023

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 () ligand was synthesized to fabricate a 3D ZnO cluster-based Zn(II)-MOF photocatalyst, Zn(TCBA)(μ-HO)HO (), which was applied to efficient photoreductive H evolution and photooxidative aerobic cross-dehydrogenation coupling reactions of -aryl-tetrahydroisoquinolines and nitromethane. In , the ingenious introduction of the meta-position benzene carboxylates on the triphenylamine motif not only promotes 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 antenna with multidimensional π interaction sites facilitate photoinduced electron transfer to render a good photocatalytic H evolution efficiency of 27.104 mmol·g·h in the presence of [Co(bpy)]Cl 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 endow with double oxygen activation ability for photocatalytic oxidation of -aryl-tetrahydroisoquinoline substrates with a yield up to 98.7% over 6 h. The durability of and the possible catalytic mechanisms were also investigated by a series of experiments including PXRD, IR, EPR, and fluorescence analyses.

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http://dx.doi.org/10.1021/acs.inorgchem.3c00763DOI Listing

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