Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer

Mátyás Imre Pápai*, Mostafa Abedi, Gianluca Levi, Elisa Biasin, Martin Meedom Nielsen, Klaus Braagaard Møller

*Corresponding author for this work

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The solvent-mediatedexcited-state dynamics of the COOH-functionalized Fe-carbene photosensitizer [Fe(bmicp)2]2+ (bmicp= 2,6-bis(3-methyl-imidazole-1-ylidine)-4-carboxy-pyridine) is studied by time-dependent density functional theory, as well as classical and quantum dynamics simulations. We demonstrate the crucial role of the polar acetonitrile solvent in stabilizing the metal-to-ligand charge transfer (MLCT) states of the investigated molecule using the conductor polarizable continuum model. This leads to dynamics that avoid sub-ps back electron transfer to the metal and an exceptionally long-lived 1MLCT state that does not undergo sub-ps 1MLCT → 3MLCT intersystem crossing as it is energetically isolated. We identify two components of the excited-state solvent reorganization process: an initial rotation (∼300 fs) and diffusional dynamics within the local cage surrounding the rotated solvent molecule (∼2 ps). Finally, it is found that the relaxation of the solvent only slightly affects the excited-state population dynamics of [Fe(bmicp)2]2+.
Original languageEnglish
JournalJournal of Physical Chemistry C
Issue number4
Pages (from-to)2056-2065
Number of pages10
Publication statusPublished - 2019

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