Issue 47, 2023

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

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 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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Aug. 2023
Accepted
30 Okt. 2023
First published
02 Nov. 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 13713-13721

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

I. B. Losada and P. Persson, Chem. Sci., 2023, 14, 13713 DOI: 10.1039/D3SC04381A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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