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 ³MLCT→³MC(³T₂g)→³MC(³T₁g)→⁵MC, and a minor ³MLCT→³MC(³T₂g)→⁵MC component. (MLCT = metal-to-ligand charge transfer, MC = metal-centered). While the direct ³MLCT→⁵MC 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 ³MC 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.