Monomer- and Ligand-Dependent Reorganization of Photoredox Pathways in Dual Photoredox/Copper ATRP
발표자
서정화 (서울대학교)
연구책임자
권민상 (서울대학교)
공동저자
서정화 (서울대학교), 권민상 (서울대학교)
초록
내용
Dual photoredox/copper catalyzed ATRP enables controlled polymerization at low copper loadings, yet the dependence of quenching pathways on the combined effects of photocatalyst (PC), ligand, and monomer remains unclear. Here, we show that quenching mechanisms reorganize across monomer classes using cyanoarene-based PCs. For methacrylates, all PCs operate via oxidative quenching, whereas for acrylates under electron-rich ligands the pathway becomes PC-dependent: 4DP-IPN and 4DMDP-IPN follow oxidative quenching, while 4Cz-IPN and 4DCDP-IPN proceed mainly via reductive quenching. Despite this divergence, 4DCDP-IPN is the most effective PC for both monomer classes, enabling controlled polymerization at ppb-level PC and ppm-level copper loadings. Acrylates also show higher oxygen sensitivity, consistent with depletion of the copper redox reservoir, establishing system-level design principles that account for ligand- and monomer-dependent pathway reorganization.