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

Mátyás Pápai*, Mostafa Abedi, Gianluca Levi, Elisa Biasin, Martin M. Nielsen, Klaus B. Møller

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)


The solvent-mediated excited-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 1 MLCT state that does not undergo sub-ps 1 MLCT → 3 MLCT 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
Pages (from-to)2056-2065
Number of pages10
JournalJournal of Physical Chemistry C
Issue number4
Publication statusPublished - 31 Jan 2019

Bibliographical note

Funding Information:
The research leading to the presented results has received funding from the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme (FP7/ 2007-2013) under REA Grant Agreement No. 609405 (COFUNDPostdocDTU), the Danish Council for Independent Research, Grant No. 4002-00272, the Independent Research Fund Denmark, Grant No. 8021-00347B, and was also supported by the “Lendület” (Momentum) Program of the Hungarian Academy of Sciences (LP2013-59). The authors are grateful for Thomas J. Penfold, Tamaś Rozgonyi, and Niels E. Henriksen for fruitful discussions.

Publisher Copyright:
Copyright © 2019 American Chemical Society.


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