Branching mechanism of photoswitching in an Fe(II) polypyridyl complex explained by full singlet-triplet-quintet dynamics

It has long been known that irradiation with visible light converts Fe(II) polypyridines from their low-spin (singlet) to high-spin (quintet) state, yet mechanistic interpretation of the photorelaxation remains controversial. Herein, we simulate the full singlet-triplet-quintet dynamics of the [Fe(terpy)(2)](2+) (terpy = 2,2’:6’,2”-terpyridine) complex in full dimension, in order to clarify the complex photodynamics. Importantly, we report a branching mechanism involving two sequential processes: a dominant (3)MLCT→(3)MC((3)T(2g))→(3)MC((3)T(1g))→(5)MC, and a minor (3)MLCT→(3)MC((3)T(2g))→(5)MC component. (MLCT = metal-to-ligand charge transfer, MC = metal-centered). While the direct (3)MLCT→(5)MC mechanism is considered as a relevant alternative, we show that it could only be operative, and thus lead to competing pathways, in the absence of (3)MC states. The quintet state is populated on the sub-picosecond timescale involving non-exponential dynamics and coherent Fe-N breathing oscillations. The results are in agreement with the available time-resolved experimental data on Fe(II) polypyridines, and fully describe the photorelaxation dynamics.