Branching mechanism of photoswitching in an Fe(II) polypyridyl complex explained by full singlet-triplet-quintet dynamics.
Commun Chem
; 6(1): 7, 2023 Jan 09.
Article
em En
| MEDLINE
| ID: mdl-36697805
ABSTRACT
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 3MLCTâ3MC(3T2g)â3MC(3T1g)â5MC, and a minor 3MLCTâ3MC(3T2g)â5MC component. (MLCT = metal-to-ligand charge transfer, MC = metal-centered). While the direct 3MLCTâ5MC 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.
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MEDLINE
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En
Ano de publicação:
2023
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Article