H/D solvent isotope effects on the photoracemization reaction of enantiomeric the tris(2,2′-bipyridine)ruthenium(ii) complex and its analogues

Literature Information

Publication Date 2020-03-02
DOI 10.1039/C9CP06758B
Impact Factor 3.676
Authors

Masahiro Asahara, Haruhiko Kurimoto, Masato Nakamizu, Shingo Hattori, Kazuteru Shinozaki


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Abstract

This work assessed solvent isotope effects on the photoracemization rate and emission lifetime for [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) in water. An analysis of the effects of temperature on photoracemization rate and emission lifetime demonstrated that the transition from one enantiomer to the other is unaffected by the isotopic composition of the solvent. The results also showed that deactivation from the metal-to-ligand charge-transfer (3MLCT) excited state to the ground state is responsible for the solvent isotope effect on the photoracemization rate. The photoracemization reaction was found to proceed via a bond-breaking mechanism. In this process, a five-coordinated species produced through breaking of the Ru–N bond in the 3d–d* state undergoes a structural change to produce an achiral five-coordinated species. An analysis of the effect of temperature on emission lifetime, excluding the activation to the 3d–d* state that leads to the structural change, showed that the solvent isotopic composition affects deactivation from the 4th MLCT state.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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