Ligand-centered to metal-centered activation of a Rh(iii) photosensitizer revealed by ab initio molecular dynamics simulations.

ABSTRACT: Excited state evolution of the rhodium(iii) complex [Rh(iii)(phen)₂(NH₃)₂]²⁺ (phen = 1,10-phenanthroline) has been investigated theoretically to gain a better understanding of light-driven activation of high-energy metal centered states. Ab initio molecular dynamics (AIMD) simulations show the significance of asymmetric motion on a multidimensional potential energy landscape around the metal center for activated crossover from triplet ligand centered (³LC) to triplet metal centered (³MC) states on picosecond timescales. Significant entropic differences arising from the structural distributions of the ³LC and ³MC states revealed by the simulations are found to favor the forward crossover process.

SUBMITTER: Losada IB 

PROVIDER: S-EPMC10699561 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature