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A Homoleptic Trisbidentate Ru(II) Complex of a Novel Bidentate Biheteroaromatic Ligand Based on Quinoline and Pyrazole Groups: Structural, Electrochemical, Photophysical, and Computational Characterization

M. Jarenmark ; L. A. Fredin ; Joachim Hedberg (Institutionen för kemi- och bioteknik, Fysikalisk kemi) ; I. Doverbratt ; P. Persson ; Maria Abrahamsson (Institutionen för kemi- och bioteknik, Fysikalisk kemi)
Inorganic Chemistry (0020-1669). Vol. 53 (2014), 24, p. 12778-12790.
[Artikel, refereegranskad vetenskaplig]

We synthesized a new homoleptic, tris-bidentate complex [Ru(QPzH)(3)](2+) based on the novel biheteroaromatic, 8-(3-pyrazolyl)-quinoline ligand QPzH. The QPzH ligand was designed to reduce the distortions typically observed in complexes incorporating the 8-quinolinyl group into the ligand framework. This was indeed observed, and was also, as anticipated, found to facilitate the formation of tris-homoleptic Ru(II) complexes; [Ru(QPzH)(3)](2+) is the first reported tris-homoleptic complex with ligands based on the 8-quinolinyl group. The synthesis can either result in a statistical 3:1 mer/fac ratio of the complex, or, through controlled exposure to light, be tweaked to allow isolation of the pure mer isomer only. X-ray crystallography reveals three nonequivalent ligands, with significantly less strain than other quinoline-based bidentate ligands. The complex exhibits a nearly octahedral coordination geometry but shows large differences in bond lengths between the Ru core and the quinoline and pyrazoles, respectively. The Ru-N(pyrazole) bond distances are similar to 2.04 angstrom, while the corresponding distances for Ru-N(quinoline) are similar to 2.12 angstrom. Structural, photophysical, electrochemical, and theoretical characterization revealed a mer-Ru(II) complex with a low oxidation potential (0.57 V vs ferrocene(0/+)) attributed to the incorporation of the pyrazolyl group, a ground state absorption that is sensitive to the local environment of the complex, and a short-lived (LCT)-L-3 excited state.

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Denna post skapades 2015-01-22. Senast ändrad 2017-09-14.
CPL Pubid: 211389


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Institutioner (Chalmers)

Institutionen för kemi- och bioteknik, Fysikalisk kemi (2005-2014)


Nanovetenskap och nanoteknik

Chalmers infrastruktur

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