Allegrezza Michael L, Konkolewicz Dominik
Department of Chemistry and Biochemmistry, Miami University, 651 East High Street, Oxford, Ohio 45056, United States.
ACS Macro Lett. 2021 Apr 20;10(4):433-446. doi: 10.1021/acsmacrolett.1c00046. Epub 2021 Mar 24.
In the past decade, photochemistry has emerged as a growing area in organic and polymer chemistry. Use of light to drive polymerization has advantages by imparting spatial and temporal control over the reaction. Photoinduced electron/energy transfer reversible addition-fragmentation chain transfer polymerization (PET-RAFT) has emerged as an excellent technique for developing well-defined polymers from a variety of functional monomers. However, the mechanism, of electron versus energy transfer is debated in the literature, with conflicting reports on the underlying process. This perspective focuses on the mechanistic aspects of PET-RAFT, in particular, the electron versus energy transfer pathways. The different mechanisms are evaluated, including evidence for one versus the other mechanisms. The current literature has not reached a consensus across all PET-RAFT processes, but rather, each catalytic system has unique characteristics.
在过去十年中，光化学已成为有机化学和高分子化学中一个不断发展的领域。利用光驱动聚合反应具有优势，因为它能对反应进行空间和时间上的控制。光致电子/能量转移可逆加成-断裂链转移聚合反应（PET-RAFT）已成为一种从多种功能单体合成结构明确聚合物的出色技术。然而，电子转移与能量转移的机制在文献中存在争议，关于其潜在过程的报道相互矛盾。本观点聚焦于PET-RAFT的机理方面，特别是电子转移与能量转移途径。对不同的机理进行了评估，包括支持一种机理而非另一种机理的证据。目前的文献尚未就所有PET-RAFT过程达成共识，相反，每个催化体系都有其独特的特性。
