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

doi:10.1021/acs.jpcc.8b10768

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 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). Lastly, it is found that the relaxation of the solvent only slightly affects the excited-state population dynamics of [Fe(bmicp)₂]²⁺.

Authors:

^[1]; Abedi, Mostafa ^[2]; Levi, Gianluca ^[3]; Biasin, Elisa ^[4]; Nielsen, Martin M. ^[2];

^[2]

Technical Univ. of Denmark, Lyngby (Denmark); Hungarian Academy of Sciences, Budapest (Hungary)
Technical Univ. of Denmark, Lyngby (Denmark)
Technical Univ. of Denmark, Lyngby (Denmark); Univ. of Ireland, Reykjavik (Ireland)
Technical Univ. of Denmark, Lyngby (Denmark); SLAC National Accelerator Lab., Menlo Park, CA (United States)

Publication Date:: 2019-01-03

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1503401

Grant/Contract Number:: AC02-76SF00515; 609405; LP2013-59; 4002-00272; 8021-00347B

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 123; Journal Issue: 4; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Pápai, Mátyás, Abedi, Mostafa, Levi, Gianluca, Biasin, Elisa, Nielsen, Martin M., and Møller, Klaus B. Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer.  United States: N. p., 2019. 
        Web.  doi:10.1021/acs.jpcc.8b10768.

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                    Pápai, Mátyás, Abedi, Mostafa, Levi, Gianluca, Biasin, Elisa, Nielsen, Martin M., & Møller, Klaus B. Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer.  United States.  doi:https://doi.org/10.1021/acs.jpcc.8b10768

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                    Pápai, Mátyás, Abedi, Mostafa, Levi, Gianluca, Biasin, Elisa, Nielsen, Martin M., and Møller, Klaus B. Thu .  
        "Theoretical Evidence of Solvent-Mediated Excited-State Dynamics in a Functionalized Iron Sensitizer".  United States.  doi:https://doi.org/10.1021/acs.jpcc.8b10768.  https://www.osti.gov/servlets/purl/1503401.

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@article{osti_1503401,

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

  author       = {Pápai, Mátyás and Abedi, Mostafa and Levi, Gianluca and Biasin, Elisa and Nielsen, Martin M. and Møller, Klaus B.},

  abstractNote = {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 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). Lastly, it is found that the relaxation of the solvent only slightly affects the excited-state population dynamics of [Fe(bmicp)2]2+.},

  doi          = {10.1021/acs.jpcc.8b10768},

  journal      = {Journal of Physical Chemistry. C},

  number       = 4,

  volume       = 123,

  place        = {United States},

  year         = {2019},

  month        = {1}

}

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DOI: https://doi.org/10.1021/acs.jpcc.8b10768

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Works referencing / citing this record:

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy
journal, October 2019

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Angewandte Chemie International Edition, Vol. 59, Issue 1
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Toward Luminescent Iron Complexes: Unravelling the Photophysics by Computing Potential Energy Surfaces
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Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering
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Nature Communications, Vol. 11, Issue 1
DOI: 10.1038/s41467-020-14468-w

Excited-state solvation structure of transition metal complexes from molecular dynamics simulations and assessment of partial atomic charge methods
journal, January 2019

Abedi, Mostafa; Levi, Gianluca; Zederkof, Diana B.
Physical Chemistry Chemical Physics, Vol. 21, Issue 7
DOI: 10.1039/c8cp06567e

Simulation of ultrafast excited-state dynamics and elastic x-ray scattering by quantum wavepacket dynamics
journal, September 2019

Pápai, Mátyás; Rozgonyi, Tamás; Penfold, Thomas J.
The Journal of Chemical Physics, Vol. 151, Issue 10
DOI: 10.1063/1.5115204

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

Abstract

Citation Formats

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy journal, October 2019

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy journal, January 2020

Toward Luminescent Iron Complexes: Unravelling the Photophysics by Computing Potential Energy Surfaces journal, May 2019

Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal, January 2020

Excited-state solvation structure of transition metal complexes from molecular dynamics simulations and assessment of partial atomic charge methods journal, January 2019

Simulation of ultrafast excited-state dynamics and elastic x-ray scattering by quantum wavepacket dynamics journal, September 2019

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy
journal, October 2019

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy
journal, January 2020

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journal, May 2019

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journal, January 2020

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journal, September 2019