Intersystem Crossing and Triplet Dynamics in an Iron(II) N-Heterocyclic Carbene Photosensitizer
| Autor: | Matthias Bauer, Leticia González, Christoph Wölper, J. Patrick Zobel, Peter Zimmer, Olga S. Bokareva |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | The electronic excited states of the iron(II) complex [FeII(tpy)(pyz-NHC)]2+ [tpy = 2,2′:6′,2″-terpyridine; pyz-NHC = 1,1′-bis(2,6-diisopropylphenyl)pyrazinyldiimidazolium-2,2′-diylidene] and their relaxation pathways have been theoretically investigated. To this purpose, trajectory surface-hopping simulations within a linear vibronic coupling model including a 244-dimensional potential energy surface (PES) with 20 singlet and 20 triplet coupled states have been used. The simulations show that, after excitation to the lowest-energy absorption band of predominant metal-to-ligand charge-transfer character involving the tpy ligand, almost 80% of the population undergoes intersystem crossing to the triplet manifold in about 50 fs, while the remaining 20% decays through internal conversion to the electronic ground state in about 300 fs. The population transferred to the triplet states is found to deactivate into two different regions of the PESs, one where the static dipole moment is small and shows increased metal-centered character and another with a large static dipole moment, where the electron density is transferred from the tpy to pyz-NHC ligand. Coherent oscillations of 400 fs are observed between these two sets of triplet populations, until the mixture equilibrates to a ratio of 60:40. Finally, the importance of selecting suitable normal modes is highlighted—a choice that can be far from straightforward in transition-metal complexes with hundreds of degrees of freedom. Trajectory surface-hopping simulations with a linear vibronic coupling model reveal the competition of major intersystem crossing versus minor internal conversion dynamics in an iron(II) N-heterocyclic carbene dye. The triplet population bifurcates into two regions of the potential energy surfaces, characterized by small and large static dipole moments due to different electronic character and showing coherent oscillations of 400 fs until both triplet populations coexist in a mixture of 60:40. |
| Databáze: | OpenAIRE |
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