Leveraging Intramolecular π-Stacking to Access an Exceptionally Long-Lived 3MC Excited State in an Fe(II) Carbene Complex

Abstract

The ability to manipulate excited-state decay cascades using molecular structure is essential to the application of abundant-metal photosensitizers and chromophores. Ligand design has yielded some spectacular results elongating charge-transfer excited state lifetimes of Fe(II) coordination complexes, but triplet metal-centered (³MC) excited states─recently demonstrated to be critical to the photoactivity of isoelectronic Co(III) polypyridyls─have to date remained elusive, with temporally isolable examples limited to the picosecond regime. With this report, we show how strong-field donors and intramolecular π-stacking can conspire to stabilize a long-lived ³MC excited state for a remarkable 4.1 ± 0.3 ns in fluid solution at ambient temperature. Analysis of variable-temperature time-resolved absorption data using theoretical models ranging from Arrhenius to semiclassical Marcus theory, combined with computational modeling and X-ray crystallography, reveal a Jahn–Teller stabilized excited state with a high activation barrier for ground-state recovery. The net result is a chromophore with a ³MC excited-state lifetime that is orders of magnitude longer than anything yet observed for an Fe(II) complex.