Environmentally persistent free radicals (EPFRs) are long-lived radicals, which can survive for weeks or even months in the environment due to resonance stabilization between an aromatic system and a metal center. To interpret this process, we use real-time time-dependent density functional theory (RT-TDDFT) to model the charge migration dynamics of EPFRs and cast these dynamics in terms of organic-like mechanisms. As a baseline, unsubstituted EPFRs with different transition metals were modeled and compared with previous experimental studies. These aromatic systems were then functionalized with electron withdrawing and donating groups to offer additional charge migration tunability. This not only yields valuable insight and control of charge migration dynamics, but also demonstrates potential pathways for reducing EPFR lifetimes.

Tunable attosecond charge migration in functionalized environmentally persistent free radicals

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.