Effect of tert-Butyl Functionalization on the Photoexcited Decay of a Fe(II)-N-Heterocyclic Carbene Complex

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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.
Original languageEnglish
JournalThe Journal of Physical Chemistry Part C
Volume120
Issue number31
Pages (from-to)17234-17241
Number of pages8
ISSN1932-7447
DOIs
Publication statusPublished - 2016
CitationsWeb of Science® Times Cited: No match on DOI

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