Substituent Effects of Fluorescein on Photoredox Initiating Performance under Visible Light

[Image: see text] We demonstrated the effects of substituents in fluorescein on the photoredox catalytic performance under visible light. For the systematic investigation, the phenyl ring of fluorescein was substituted with six different functional groups (i.e., amine, amide, isothiocyanate, aminomethyl, bromo, or nitro group) at the 5- or 6-position. The fluorescein derivatives were carefully characterized through photophysical and electrochemical analyses. The substituent effects were estimated by comparing the photopolymerization of poly(ethylene glycol) diacrylate (PEGDA) and N-vinylpyrrolidone (VP) in the presence of triethanolamine (TEOA) under aerobic conditions to that of intact fluorescein. As a result, the amine and nitro groups exhibited the lowest performances, presumably due to intramolecular photoinduced electron transfer (PET) promoted by the strong electron push–pull effect. The others, representative moderate or weak deactivators and activators, exhibited inferior performances than intact fluorescein, presumably owing to the more negative ΔG(PET) values, resulting in a decreased rate of intermolecular PET. These results are crucial for understanding the structure–performance relationship and the development of visible-light photoredox catalysts with improved performance and functionality.