Highly Fluorinated Ir(III)–2,2′:6′,2″-Terpyridine–Phenylpyridine–X Complexes via Selective C–F Activation: Robust Photocatalysts for Solar Fuel Generation and Photoredox Catalysis

摘要: A series of fluorinated Ir(III)–terpyridine–phenylpyridine–X (X = anionic monodentate ligand) complexes were synthesized by selective C–F activation, whereby perfluorinated phenylpyridines readily complexed. The combination phenylpyridine ligands with an electron-rich tri-tert-butyl terpyridine ligand generates a “push–pull” force on the electrons upon excitation, imparting significant enhancements to stability, electrochemical, and photophysical properties complexes. Application as photosensitizers for photocatalytic generation hydrogen from water redox photocatalysts decarboxylative fluorination several carboxylic acids showcases performance in highly coordinating solvents, some cases exceeding that leading photosensitizers. Changes nature excited states are observed compounds increase well exchange ancillary chloride liga...