Exploration of Uncharted 3PES Territory for [Ru(bpy)3]2+: A New 3MC Minimum Prone to Ligand Loss Photochemistry

Adrien Soupart, Fabienne Alary, Jean-Louis Heully, Paul Elliott, Isabelle M. Dixon

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

We have identified a new 3MC state bearing two elongated Ru–N bonds to the same ligand in [Ru(bpy)3]2+. This DFT-optimized structure is a local minimum on the 3PES. This distal MC state (3MCcis) is destabilized by less than 2 kcal/mol with respect to the classical MC state (3MCtrans), and energy barriers to populate 3MCcis and 3MCtrans from the 3MLCT state are similar according to nudged elastic band minimum energy path calculations. Distortions in the classical 3MCtrans, that is, elongation of two Ru–N bonds toward two different bpy ligands, are not expected to favor the formation of ligand-loss photoproducts. On the contrary, the new 3MCcis could be particularly relevant in the photodegradation of Ru(II) polypyridine complexes.
LanguageEnglish
Pages3192-3196
Number of pages5
JournalInorganic Chemistry
Volume57
Issue number6
Early online date6 Mar 2018
DOIs
Publication statusPublished - 19 Mar 2018

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Photochemical reactions
photochemical reactions
Ligands
ligands
Bearings (structural)
Energy barriers
Photodegradation
Discrete Fourier transforms
elongation
Elongation
energy
tris(2,2'-bipyridine)ruthenium II

Cite this

Soupart, Adrien ; Alary, Fabienne ; Heully, Jean-Louis ; Elliott, Paul ; Dixon, Isabelle M. / Exploration of Uncharted 3PES Territory for [Ru(bpy)3]2+: A New 3MC Minimum Prone to Ligand Loss Photochemistry. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 6. pp. 3192-3196.
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abstract = "We have identified a new 3MC state bearing two elongated Ru–N bonds to the same ligand in [Ru(bpy)3]2+. This DFT-optimized structure is a local minimum on the 3PES. This distal MC state (3MCcis) is destabilized by less than 2 kcal/mol with respect to the classical MC state (3MCtrans), and energy barriers to populate 3MCcis and 3MCtrans from the 3MLCT state are similar according to nudged elastic band minimum energy path calculations. Distortions in the classical 3MCtrans, that is, elongation of two Ru–N bonds toward two different bpy ligands, are not expected to favor the formation of ligand-loss photoproducts. On the contrary, the new 3MCcis could be particularly relevant in the photodegradation of Ru(II) polypyridine complexes.",
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Exploration of Uncharted 3PES Territory for [Ru(bpy)3]2+: A New 3MC Minimum Prone to Ligand Loss Photochemistry. / Soupart, Adrien; Alary, Fabienne; Heully, Jean-Louis; Elliott, Paul; Dixon, Isabelle M.

In: Inorganic Chemistry, Vol. 57, No. 6, 19.03.2018, p. 3192-3196.

Research output: Contribution to journalArticle

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AB - We have identified a new 3MC state bearing two elongated Ru–N bonds to the same ligand in [Ru(bpy)3]2+. This DFT-optimized structure is a local minimum on the 3PES. This distal MC state (3MCcis) is destabilized by less than 2 kcal/mol with respect to the classical MC state (3MCtrans), and energy barriers to populate 3MCcis and 3MCtrans from the 3MLCT state are similar according to nudged elastic band minimum energy path calculations. Distortions in the classical 3MCtrans, that is, elongation of two Ru–N bonds toward two different bpy ligands, are not expected to favor the formation of ligand-loss photoproducts. On the contrary, the new 3MCcis could be particularly relevant in the photodegradation of Ru(II) polypyridine complexes.

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