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Title: On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer

Abstract

Copper(I) bis-phenanthroline complexes represent Earth-abundant alternatives to ruthenium-based sensitizers for solar energy conversion and photocatalysis. Improved understanding of the solvent-mediated excited-state structural dynamics can help optimize their photoconversion efficiency. Through direct dynamics simulations in acetonitrile and excited-state minimum energy path calculations in vacuum, we uncover the mechanism of the photoinduced flattening motion of the prototypical system [Cu(dmphen)2]+ (dmphen = 2,9-dimethyl-1,10-phenanthroline). We find that the ligand distortion is a two-step process in acetonitrile. We report the fast component (~110 fs) is due to spontaneous pseudo Jahn–Teller instability and is largely solvent independent, while the slow component (~1.2 ps) arises from the mutual interplay between solvent molecules closely approaching the metal center and rotation of the methyl substituents. These results shed new light on the influence of a donor solvent such as acetonitrile and methyl substituents on the flattening dynamics of [Cu(dmphen)2]+.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Iceland, Reykjavik (Iceland)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); Icelandic Research Fund (IRF)
OSTI Identifier:
1604759
Grant/Contract Number:  
AC02-76SF00515; 196070-051; 196279-051
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 22; Journal Issue: 2; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Levi, Gianluca, Biasin, Elisa, Dohn, Asmus O., and Jónsson, Hannes. On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer. United States: N. p., 2019. Web. doi:10.1039/c9cp06086c.
Levi, Gianluca, Biasin, Elisa, Dohn, Asmus O., & Jónsson, Hannes. On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer. United States. doi:https://doi.org/10.1039/c9cp06086c
Levi, Gianluca, Biasin, Elisa, Dohn, Asmus O., and Jónsson, Hannes. Thu . "On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer". United States. doi:https://doi.org/10.1039/c9cp06086c. https://www.osti.gov/servlets/purl/1604759.
@article{osti_1604759,
title = {On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer},
author = {Levi, Gianluca and Biasin, Elisa and Dohn, Asmus O. and Jónsson, Hannes},
abstractNote = {Copper(I) bis-phenanthroline complexes represent Earth-abundant alternatives to ruthenium-based sensitizers for solar energy conversion and photocatalysis. Improved understanding of the solvent-mediated excited-state structural dynamics can help optimize their photoconversion efficiency. Through direct dynamics simulations in acetonitrile and excited-state minimum energy path calculations in vacuum, we uncover the mechanism of the photoinduced flattening motion of the prototypical system [Cu(dmphen)2]+ (dmphen = 2,9-dimethyl-1,10-phenanthroline). We find that the ligand distortion is a two-step process in acetonitrile. We report the fast component (~110 fs) is due to spontaneous pseudo Jahn–Teller instability and is largely solvent independent, while the slow component (~1.2 ps) arises from the mutual interplay between solvent molecules closely approaching the metal center and rotation of the methyl substituents. These results shed new light on the influence of a donor solvent such as acetonitrile and methyl substituents on the flattening dynamics of [Cu(dmphen)2]+.},
doi = {10.1039/c9cp06086c},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 2,
volume = 22,
place = {United States},
year = {2019},
month = {12}
}

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