Two-Dimensional Porphyrinic Metal-Organic Framework Composites as a Photocatalytic Platform for Chemoselective Hydrogenation.

Chemoselective hydrogenation with high efficiency under ambient conditions remains a great challenge. Herein, an efficient photocatalyst, the 2D porphyrin metal-organic framework composite AmPy/Pd-PPF-1(Cu), featuring AmPy (1-aminopyrene) sitting axially on a paddle-wheel unit, has been rationally fabricated. The 2D AmPy/Pd-PPF-1(Cu) composite acts as a photocatalytic platform, promoting the selective hydrogenation of quinolines to tetrahydroquinolines with a yield up to 99%, in which ammonia borane serves as the hydrogen donor. The AmPy molecules coordinated on a 2D MOF not only enhance the light absorption capacity but also adjust the layer spacing without affecting the network structure of 2D Pd-PPF-1(Cu) nanosheets. Through deuterium-labeling experiments, in situ X-ray photoelectron spectroscopy, electron paramagnetic resonance studies, and density functional theory calculations, it is disclosed that Cu paddle-wheel units in 2D AmPy/Pd-PPF-1(Cu) nanosheets behave as the active site for transfer hydrogenation, and metalloporphyrin ligand and axial aminopyrene molecules can enhance the light absorption capacity and excite photogenerated electrons to Cu paddle-wheel units, assisting in photocatalysis.