Publications
Guidelines to calculate non-radiative deactivation mechanisms of ruthenium tris(bipyridine) derivatives
- Author(s)
- David Hernández-Castillo, Isabel Eder, Leticia González
- Abstract
The applicability of ruthenium tris(bipyridine) complexes in fields like photoactivated chemotherapy or photocatalysis requires in-depth understanding of their excited state deactivation mechanism. In particular, the quenching of luminescence from the lowest triplet metal-to-ligand charge-transfer ([Formula presented]) excited state or the ligand photorelease relies on the fine-tuning of the energetics of the higher-lying metal-centered excited states ([Formula presented]). In this contribution, we critically review different kinetic models commonly used to interpret the thermal activation of the [Formula presented] excited states from the lowest [Formula presented] minimum. Further, we extend our recently introduced kinetic model (Angew. Chem. Int. Ed. 2023, 62, e202308803) for [Formula presented] (bpy = 2,2'-bipyridine) to a set of homoleptic tris(bipyridine)ruthenium (II) derivatives. This set has been selected to cover a wide range of electron -withdrawing/-donating substituents in the periphery of the bipyridyl ligands (4,4'-[Formula presented]-2,2'-bpy; R= [Formula presented], [Formula presented], [Formula presented], [Formula presented], [Formula presented] [Formula presented], and [Formula presented]), on the basis of the Hammett's constant of the R functional group. Our calculations show that complexes with electron donating groups decay predominantly via one Jahn-Teller isomer (the so-called [Formula presented] -trans conformation), while those with electron withdrawing ligands tend to decay through a different one (the [Formula presented]-cis Jahn-Teller isomer). We discuss structure/property relationships with focus on how to steer the energetics of the [Formula presented] excited states. This work opens the pathway to rationally use ligand substitution to enhance or quench the lifetimes of the [Formula presented] state and also provides guidelines to understand better non-radiative deactivation mechanisms in metal complexes.
- Organisation(s)
- Department of Theoretical Chemistry, Research Platform Accelerating Photoreaction Discovery
- External organisation(s)
- Vienna Doctoral School in Chemistry (DoSChem)
- Journal
- Coordination Chemistry Reviews
- Volume
- 510
- ISSN
- 0010-8545
- DOI
- https://doi.org/10.1016/j.ccr.2024.215819
- Publication date
- 07-2024
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 104017 Physical chemistry, 104022 Theoretical chemistry
- Keywords
- ASJC Scopus subject areas
- Chemistry(all), Physical and Theoretical Chemistry, Inorganic Chemistry, Materials Chemistry
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/guidelines-to-calculate-nonradiative-deactivation-mechanisms-of-ruthenium-trisbipyridine-derivatives(e05bb419-475e-4e2c-a537-00dab8c69578).html