Phosphonium Tetraphenylborate: A Photocatalyst for Visible-Light-Induced, Nucleophile-Initiated Thiol-Michael Addition Photopolymerization.

A photoinitiation system that utilizes phosphonium tetraphenylborate as the key component was developed for the visible light-triggered nucleophile-catalyzed thiol-Michael addition reaction. This highly reactive catalyst was composed of a photocaged phosphine (methyldiphenylphosphonium tetraphenylborate, MDPP·HBPh 4 ), a photosensitizer (isopropylthioxanthone, ITX), and a radical scavenger (TEMPO). Unlike the prevailing photobase catalysts, this photoactivatable phosphine system triggers the thiol-Michael addition polymerization by a nucleophile-catalyzed mechanism and provides a controlled stoichiometric reaction between the thiol and the vinyl precursors. This approach enables the formation of homogeneous polymer networks upon low-energy visible light exposure and, thus, broadens its potential applications in bulk polymer materials synthesis and UV-sensitive bioscaffold formation.