Effect of delocalization and rigidity in the acceptor ligand on MLCT excited-state decay
Abstract
In its most simple form, the energy gap law for excited-state nonradiative decay predicts a linear dependence of ln k(nr) on the ground- to excited-state energy gap, where k(nr) is the rate constant for nonradiative decay. At this level of approximation, the energy gap law has been successfully applied to nonradiative decay in a wide array of MLCT excited states of polypyridyl complexes of Re(I), Ru(II), and Os(II). This relationship also predicts a dependence of k(nr) on the structural characteristics of the acceptor ligand. We report here a brief survey of the literature which suggests that such effects exist and have their origin in the extent of delocalization of the excited electron in the ligand pi framework and on acceptor ligand rigidity.
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The difficulty in constructing NIR emission lies in the rapid internal conversion between low-energy-level S1 and S0, explored in light of the energy-gap law.
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Red-light excited efficient metal-free near-infrared room-temperature phosphorescent films
Sun, S., Ma, L., Wang, J., Ma, X., & Tian, H. (2022) · National Science Review · doi:10.1093/nsr/nwab085 · Cited by 108 · see citing works
- Authors
- Treadway, J. A., Loeb, B., Lopez, R., Anderson, P. A., Keene, F. R., & Meyer, T. J.
- Affiliations
- Pontificia Universidad Católica de Chile (CL)
- Department of Chemistry, The University of North Carolina, CB#3290, Chapel Hill, North Carolina 27599-3290, Faculty of Chemistry, Pontificia Universidad Catolica de Chile, Casilla 306, Buzon 521, Santiago, Chile, and Department of Molecular Sciences, James Cook University of North Queensland, Townsville, Queensland 4811, Australia
- Venue
- Inorganic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 1996-01-01
- Volume
- 35
- Issue
- 8
- Pages
- 2242-2246
- ISSN
- 0020-1669 (ISSN-L)
- 1520-510X
- OpenAlex
- W2088407745
- Cited by
- 249
- References
- 137
- Citations by year
- 2026: 4 · 2025: 7 · 2024: 9 · 2023: 4 · 2022: 8 · 2021: 9 · 2020: 11 · 2019: 4 · 2018: 3 · 2017: 7 · 2016: 13 · 2015: 8 · 2014: 7 · 2013: 7 · 2012: 10
- FWCI
- 6.77
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Inorganic Chemistry (publishedVersion)
- PubMed (publishedVersion)
- ResearchOnline - JCU (James Cook University) (submittedVersion)
- Topics
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Organic Light-Emitting Diodes Research
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Keywords
- MLCT excited states, nonradiative decay, energy gap law, polypyridyl complexes, metal-to-ligand charge transfer, excited-state decay kinetics, ruthenium(II) complexes, osmium(II) complexes, rhenium(I) complexes
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