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

doi:10.1021/acs.jpcc.8b10768

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

Science Institute

University of Iceland, Iceland

Research output: Contribution to journal › Article › peer-review

16 Citations (Scopus)

Abstract

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 language	English
Pages (from-to)	2056-2065
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	123
Issue number	4
DOIs	https://doi.org/10.1021/acs.jpcc.8b10768
Publication status	Published - 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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10.1021/acs.jpcc.8b10768

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title = "Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer",

abstract = " 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+ . ",

author = "M{\'a}ty{\'a}s P{\'a}pai and Mostafa Abedi and Gianluca Levi and Elisa Biasin and Nielsen, {Martin M.} and M{\o}ller, {Klaus B.}",

note = "Funding Information: The research leading to the presented results has received funding from the People Programme (Marie Curie Actions) of the European Union{\textquoteright}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 “Lend{\"u}let” (Momentum) Program of the Hungarian Academy of Sciences (LP2013-59). The authors are grateful for Thomas J. Penfold, Tama{\'s} Rozgonyi, and Niels E. Henriksen for fruitful discussions. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

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AU - Levi, Gianluca

AU - Biasin, Elisa

AU - Nielsen, Martin M.

AU - Møller, Klaus B.

N1 - 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.

PY - 2019/1/31

Y1 - 2019/1/31

N2 - 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+ .

AB - 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+ .

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

Abstract

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