Journal article
Effect of tert-Butyl Functionalization on the Photoexcited Decay of a Fe(II)-N-Heterocyclic Carbene Complex
Department of Chemistry1
Wigner Research Centre for Physics, Hungarian Academy of Sciences, “Lendület” (Momentum) Spectroscopy Research Group, P.O. Box 49, H-1525 Budapest2
School of Chemistry3
Understanding and subsequently being able to manipulate the excited-state decay pathways of functional transition-metal complexes is of utmost importance in order to solve grand challenges in solar energy conversion and data storage. Herein, we perform quantum chemical calculations and spin-vibronic quantum dynamics simulations on the Fe-N-heterocyclic carbene complex, [Fe(btbip)2]2+ (btbip = 2,6-bis(3-tert-butyl-imidazole-1-ylidene)pyridine). The results demonstrate that a relatively minor structural change compared to its parent complex, [Fe(bmip)2]2+ (bmip = 2,6-bis(3-methyl-imidazole-1-ylidene)pyridine), completely alters the excited-state relaxation.
Ultrafast deactivation of the initially excited metal-to-ligand charge transfer (1,3MLCT) states occurs within 350 fs. In contrast to the widely adopted mechanism of Fe(II) photophysics, these states decay into close-lying singlet metal-centered (1MC) states. This occurs because the tert-butyl functionalization stabilizes the 1MC states, enabling the 1,3MLCT → 1MC population transfer to occur close to the Franck–Condon geometry, making the conversion very efficient.
Subsequently, a spin cascade occurs within the MC manifold, leading to the population of triplet and quintet MC states. These results will inspire highly involved ultrafast experiments performed at X-ray free electron lasers and shall pave the way for the design of novel high-efficiency transition-metal-based functional molecules.
Language: | English |
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Publisher: | American Chemical Society |
Year: | 2016 |
Pages: | 17234-17241 |
ISSN: | 19327455 and 19327447 |
Types: | Journal article |
DOI: | 10.1021/acs.jpcc.6b05023 |