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Excited State Dynamics of Bistridentate and Trisbidentate RuII Complexes of Quinoline-Pyrazole Ligands

Fredin, Lisa LU ; Hedberg Wallenstein, Joachim ; Sundin, Elin ; Jarenmark, Martin LU ; Barbosa de Mattos, Deise F. ; Persson, Petter LU and Abrahamsson, Maria (2019) In Inorganic Chemistry 58(24). p.16354-16363
Abstract
Three homoleptic ruthenium(II) complexes, [Ru(Q3PzH)3]2+, [Ru(Q1Pz)3]2+, and [Ru(DQPz)2]2+, based on the quinoline–pyrazole ligands, Q3PzH (8-(3-pyrazole)-quinoline), Q1Pz (8-(1-pyrazole)-quinoline), and DQPz (bis(quinolinyl)-1,3-pyrazole), have been spectroscopically and theoretically investigated. Spectral component analysis, transient absorption spectroscopy, density functional theory calculations, and ligand exchange reactions with different chlorination agents reveal that the excited state dynamics for Ru(II) complexes with these biheteroaromatic ligands differ significantly from that of traditional polypyridyl complexes. Despite the high energy and low reorganization energy of the excited state, nonradiative decay dominates even at... (More)
Three homoleptic ruthenium(II) complexes, [Ru(Q3PzH)3]2+, [Ru(Q1Pz)3]2+, and [Ru(DQPz)2]2+, based on the quinoline–pyrazole ligands, Q3PzH (8-(3-pyrazole)-quinoline), Q1Pz (8-(1-pyrazole)-quinoline), and DQPz (bis(quinolinyl)-1,3-pyrazole), have been spectroscopically and theoretically investigated. Spectral component analysis, transient absorption spectroscopy, density functional theory calculations, and ligand exchange reactions with different chlorination agents reveal that the excited state dynamics for Ru(II) complexes with these biheteroaromatic ligands differ significantly from that of traditional polypyridyl complexes. Despite the high energy and low reorganization energy of the excited state, nonradiative decay dominates even at liquid nitrogen temperatures, where triplet metal-to-ligand-charge-transfer emission quantum yields range from 0.7 to 3.8%, and microsecond excited state lifetimes are observed. In contrast to traditional polypyridyl complexes where ligand exchange is facilitated by expansion of the metal–ligand bonds to stabilize a metal-centered state, photoinduced ligand exchange occurs in the bidentate complexes despite no substantial MC state population, while the tridentate complex is extremely photostable despite an activated decay route, highlighting the versatile photochemistry of nonpolypyridine ligands. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
58
issue
24
pages
16354 - 16363
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85076237908
  • pmid:31800221
ISSN
1520-510X
DOI
10.1021/acs.inorgchem.9b01543
language
English
LU publication?
yes
id
49341d3e-7684-4afb-9b6f-192e27f1d7da
date added to LUP
2020-02-19 09:55:25
date last changed
2023-11-20 00:51:54
@article{49341d3e-7684-4afb-9b6f-192e27f1d7da,
  abstract     = {{Three homoleptic ruthenium(II) complexes, [Ru(Q3PzH)3]2+, [Ru(Q1Pz)3]2+, and [Ru(DQPz)2]2+, based on the quinoline–pyrazole ligands, Q3PzH (8-(3-pyrazole)-quinoline), Q1Pz (8-(1-pyrazole)-quinoline), and DQPz (bis(quinolinyl)-1,3-pyrazole), have been spectroscopically and theoretically investigated. Spectral component analysis, transient absorption spectroscopy, density functional theory calculations, and ligand exchange reactions with different chlorination agents reveal that the excited state dynamics for Ru(II) complexes with these biheteroaromatic ligands differ significantly from that of traditional polypyridyl complexes. Despite the high energy and low reorganization energy of the excited state, nonradiative decay dominates even at liquid nitrogen temperatures, where triplet metal-to-ligand-charge-transfer emission quantum yields range from 0.7 to 3.8%, and microsecond excited state lifetimes are observed. In contrast to traditional polypyridyl complexes where ligand exchange is facilitated by expansion of the metal–ligand bonds to stabilize a metal-centered state, photoinduced ligand exchange occurs in the bidentate complexes despite no substantial MC state population, while the tridentate complex is extremely photostable despite an activated decay route, highlighting the versatile photochemistry of nonpolypyridine ligands.}},
  author       = {{Fredin, Lisa and Hedberg Wallenstein, Joachim and Sundin, Elin and Jarenmark, Martin and Barbosa de Mattos, Deise F. and Persson, Petter and Abrahamsson, Maria}},
  issn         = {{1520-510X}},
  language     = {{eng}},
  month        = {{12}},
  number       = {{24}},
  pages        = {{16354--16363}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Inorganic Chemistry}},
  title        = {{Excited State Dynamics of Bistridentate and Trisbidentate RuII Complexes of Quinoline-Pyrazole Ligands}},
  url          = {{http://dx.doi.org/10.1021/acs.inorgchem.9b01543}},
  doi          = {{10.1021/acs.inorgchem.9b01543}},
  volume       = {{58}},
  year         = {{2019}},
}