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Ligand-centered to metal-centered activation of a Rh(iii) photosensitizer revealed by ab initio molecular dynamics simulations

Losada, Iria Bolaño LU and Persson, Petter LU (2023) In Chemical Science 14(47). p.13713-13721
Abstract

Excited state evolution of the rhodium(iii) complex [Rh(iii)(phen)2(NH3)2]2+ (phen = 1,10-phenanthroline) has been investigated theoretically to gain a better understanding of light-driven activation of high-energy metal centered states. Ab initio molecular dynamics (AIMD) simulations show the significance of asymmetric motion on a multidimensional potential energy landscape around the metal center for activated crossover from triplet ligand centered (3LC) to triplet metal centered (3MC) states on picosecond timescales. Significant entropic differences arising from the structural distributions of the 3LC and 3MC states revealed by the simulations are... (More)

Excited state evolution of the rhodium(iii) complex [Rh(iii)(phen)2(NH3)2]2+ (phen = 1,10-phenanthroline) has been investigated theoretically to gain a better understanding of light-driven activation of high-energy metal centered states. Ab initio molecular dynamics (AIMD) simulations show the significance of asymmetric motion on a multidimensional potential energy landscape around the metal center for activated crossover from triplet ligand centered (3LC) to triplet metal centered (3MC) states on picosecond timescales. Significant entropic differences arising from the structural distributions of the 3LC and 3MC states revealed by the simulations are found to favor the forward crossover process. Simulations at different temperatures provide further insight into the interplay between structural and electronic factors governing the 3LC → 3MC dynamics as a concerted two-electron energy transfer process, and the broader implications for photoinduced generation of high-energy 3MC states of interest for emerging photocatalytic applications are outlined.

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author
and
organization
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type
Contribution to journal
publication status
published
subject
in
Chemical Science
volume
14
issue
47
pages
9 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85176728873
  • pmid:38075662
ISSN
2041-6520
DOI
10.1039/d3sc04381a
language
English
LU publication?
yes
id
492431b6-39a8-480b-a5b0-724b209a90a5
date added to LUP
2024-01-10 13:50:17
date last changed
2024-06-20 14:59:23
@article{492431b6-39a8-480b-a5b0-724b209a90a5,
  abstract     = {{<p>Excited state evolution of the rhodium(iii) complex [Rh(iii)(phen)<sub>2</sub>(NH<sub>3</sub>)<sub>2</sub>]<sup>2+</sup> (phen = 1,10-phenanthroline) has been investigated theoretically to gain a better understanding of light-driven activation of high-energy metal centered states. Ab initio molecular dynamics (AIMD) simulations show the significance of asymmetric motion on a multidimensional potential energy landscape around the metal center for activated crossover from triplet ligand centered (<sup>3</sup>LC) to triplet metal centered (<sup>3</sup>MC) states on picosecond timescales. Significant entropic differences arising from the structural distributions of the <sup>3</sup>LC and <sup>3</sup>MC states revealed by the simulations are found to favor the forward crossover process. Simulations at different temperatures provide further insight into the interplay between structural and electronic factors governing the <sup>3</sup>LC → <sup>3</sup>MC dynamics as a concerted two-electron energy transfer process, and the broader implications for photoinduced generation of high-energy <sup>3</sup>MC states of interest for emerging photocatalytic applications are outlined.</p>}},
  author       = {{Losada, Iria Bolaño and Persson, Petter}},
  issn         = {{2041-6520}},
  language     = {{eng}},
  month        = {{11}},
  number       = {{47}},
  pages        = {{13713--13721}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Chemical Science}},
  title        = {{Ligand-centered to metal-centered activation of a Rh(iii) photosensitizer revealed by ab initio molecular dynamics simulations}},
  url          = {{http://dx.doi.org/10.1039/d3sc04381a}},
  doi          = {{10.1039/d3sc04381a}},
  volume       = {{14}},
  year         = {{2023}},
}