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金属萘酞菁介导的三硫代碳酸酯选择性光活化及利用热能克服活化障碍
作者:小柯机器人 发布时间:2022/1/12 10:39:26

青岛大学刘敬权团队报道了金属萘酞菁介导的三硫代碳酸酯选择性光活化及利用热能克服活化障碍。相关研究成果发表在2022年1月10日出版的《美国化学会杂志》。

金属萘酞菁(MNCs)被证明是激活光诱导电子转移可逆加成-断裂链转移(PET-RAFT)聚合的有效光催化剂,能够在近红外(λ=780 nm)光下实现(甲基)丙烯酸酯的良好控制聚合。由于三硫代碳酸酯RAFT试剂的氧化还原电位低于先前探索的光催化剂,因此其活化表现出独特的选择性,这取决于R基团的性质。具体而言,MNCs能够激活第三R族三硫代碳酸酯,而未观察到具有第二R族的三硫代碳酸酯的激活。

综合密度泛函理论计算和实验研究揭示了PET-RAFT机制控制因素的新机理,并解释了MNCs对三硫代碳酸三酯的独特选择性。有趣的是,通过适度提高反应温度(即~-15℃),克服了阻碍具有二级R基团的三硫代碳酸酯光活化的能垒,使其能够成功活化。

附:英文原文

Title: Selective Photoactivation of Trithiocarbonates Mediated by Metal Naphthalocyanines and Overcoming Activation Barriers Using Thermal Energy

Author: Zilong Wu, Kenward Jung, Chenyu Wu, Gervase Ng, Lei Wang, Jingquan Liu, Cyrille Boyer

Issue&Volume: January 10, 2022

Abstract: Metal naphthalocyanines (MNcs) were demonstrated to be efficient photocatalysts to activate photoinduced electron-transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization, enabling well-controlled polymerization of (meth)acrylates under near-infrared (λ = 780 nm) light. Owing to their lower redox potential compared to previously explored photocatalysts, the activation of trithiocarbonate RAFT agents exhibited a unique selectivity that was dependent on the nature of the R group. Specifically, MNcs were capable in activating tertiary R group trithiocarbonates, whereas no activation of the trithiocarbonate possessing a secondary R group was observed. The combination of density functional theory calculations and experimental studies have revealed new mechanistic insights into the factors governing a PET-RAFT mechanism and explained this unique selectivity of MNcs toward tertiary carbon trithiocarbonates. Interestingly, by increasing the reaction temperature moderately (i.e., ~15 °C), the energy barrier prohibiting the photoactivation of the trithiocarbonate with a secondary R group was overcome, enabling their successful activation.

DOI: 10.1021/jacs.1c11700

Source: https://pubs.acs.org/doi/10.1021/jacs.1c11700

 

期刊信息

JACS:《美国化学会志》,创刊于1879年。隶属于美国化学会,最新IF:14.612
官方网址:https://pubs.acs.org/journal/jacsat
投稿链接:https://acsparagonplus.acs.org/psweb/loginForm?code=1000