Heteroleptic Copper(I) Complexes with Pyridine-Benzothiazole Ligands as Photocatalysts for Free Radical Photopolymerization and 3D Printing

作者：Naralyne M. Pesqueira, Fabrice Morlet‐Savary, Michael Schmitt, Abdelaziz Jouaiti, Beatriz E. Goi, Matteo Mauro, Jacques Lalevée · 发表于：ACS Applied Polymer Materials · 年份：2025 · DOI：10.1021/acsapm.4c04066 · 被引用次数：7 · 研究领域：Photopolymerization techniques and applications、Advanced Polymer Synthesis and Characterization、Radical Photochemical Reactions

Copper(I) complexes have attracted considerable attention as efficient redox photocatalysts (PCs) in photopolymerization. In this study, two copper(I) complexes bearing a pyridine-benzothiazole ligand were thoroughly investigated as photocatalysts for the free radical photopolymerization of ethoxylated trimethylolpropane triacrylate under violet and green light irradiation. A three-component system comprising a copper complex, di- tert -butyl-diphenyl iodonium hexafluorophosphate, and ethyl dimethylaminobenzoate as additives was investigated under various conditions. The copper complexes exhibited remarkable photoinitiation capabilities, achieving high monomer conversion rates and highlighting significant structure–reactivity relationships. Based on free energy calculations and spectroscopic analyses, a mechanistic pathway was proposed. The optimal conditions were successfully applied in 3D printing, producing smooth and uniform 3D structures.