Excited State Dynamics of Bistridentate and Trisbidentate RuII Complexes of Quinoline-Pyrazole Ligands
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/49341d3e-7684-4afb-9b6f-192e27f1d7da
- author
- Fredin, Lisa LU ; Hedberg Wallenstein, Joachim ; Sundin, Elin ; Jarenmark, Martin LU ; Barbosa de Mattos, Deise F. ; Persson, Petter LU and Abrahamsson, Maria
- organization
- publishing date
- 2019-12-04
- 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}}, }