Investigation and Enhancement of the Stability and Performance of Water Reduction Systems based on Cyclometalated Iridium(III) Complexes

Water reduction systems that use a bis-cyclometalated Ir-III photosensitiser (PS) along with homogeneous Pd complexes as a source of in-situ-formed colloidal Pd as the water reducing complex (WRC) and triethylamine (TEA) as the sacrificial electron donor were tested and characterised with respect to their photocatalytic H-2 production performance. It was confirmed that substitution of the 2-(pyridin-2-yl)benzen-1-ide (pyb) ligand in the well-known system [Ir(pyb)(2)(bpy)](+) (bpy=2,2'-bipyridine) by the fluorinated cyclometalating ligand 5-fluoro-2-(5-methylpyridin-2-yl)benzen-1-ide (Fmpyb) tremendously enhanced the H-2 production rate. Moreover, variation of the bidentate N boolean AND N ligand bpy by alkyl substitution in the 4,4'-position resulted in an increase in the H-2 production yield by a factor of three. The incident-photon-to-hydrogen-efficiency could be enhanced from 2.6 to 12.3%. Furthermore, a new dinuclear Co complex was used as a reduction catalyst and showed up to 760 turnovers after 20 h. A detailed study of the concentration impact of all components in the photoredox system was performed. DFT calculations were used to aid the explanation of the findings.