Targeted Modulation of Photocatalytic Hydrogen Evolution Activity by Nickel-Substituted Rubredoxin through Functionalized Ruthenium Phototriggers.

Light-driven hydrogen evolution is a promising means of sustainable energy production to meet global energy demand. This study investigates the photocatalytic hydrogen evolution activity of nickel-substituted rubredoxin (NiRd), an artificial hydrogenase mimic, covalently attached to a ruthenium phototrigger (RuNiRd). By systematically modifying the para-substituents on Ru(II) polypyridyl complexes, we sought to optimize the intramolecular electron transfer processes within the RuNiRd system. A series of electron-donating and electron-withdrawing groups were introduced to tune the photophysical, photochemical, and electrochemical properties of the ruthenium complexes. Our findings reveal that electron-donating substituents can increase the hydrogen evolution capabilities of the artificial enzyme to a point; however, the complexes with the most electron-donating substituents suffer from short lifetimes and inefficient reductive quenching, rendering them inactive. The present work highlights the intricate balance required between driving force, lifetime, and quenching efficiency for effective light-driven catalysis, providing valuable insights into the design of artificial enzyme-photosensitizer constructs.