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Investigating the effects of supramolecularly caging ligands in [Ru(bpy)2L]2+ complexes

journal contribution
posted on 2017-06-16, 08:24 authored by Edwin C. Constable, Catherine E. Housecroft, Peter Kopecky, Colin J. Martin, Iain Wright, Jennifer A. Zampese
Five ruthenium(II) complexes [Ru(bpy)2(L)][PF6] 2 in which L is a 6-substituted 2,2′-bipyridine ligand (ligands 1-3), 5-(2-picoloyl) (4), or an N,O-donor (5) have been prepared and characterized to investigate the role of the intramolecular caging effect of pendant aryl-substituents on the electronic and photophysical properties. The single crystal structures of three of the complexes are reported; in [Ru(bpy)2(L)][PF6]2 where L = 6-(selenophen-2-yl)-2,2′-bipyridine, intra-cation face-to-face π-stacking of the selenophenyl unit and one pyridine ring of an adjacent ligand is observed. In comparison to [Ru(bpy)3]2+, the energy of the MLCT band in [Ru(bpy)2(L)]2+ for L = 1, 2, 3 or 4 is little affected, but a red-shift of 35 nm is observed for [Ru(bpy) 2(5)]2+. The new complexes are emissive at room temperature in degassed MeCN solution; values of λmaxem range from 613 to 689 nm for [Ru(bpy)2(L)]2+ (L = 1 to 5). The electrochemical behaviour of [Ru(bpy)2(L)][PF 6]2 for L = 1, 2 and 3 is similar; in contrast, [Ru(bpy)2(4)][PF6]2 exhibits more complicated ligand-based redox behaviour, and for [Ru(bpy)2(5)][PF 6]2, the presence of the N,O-donor shifts the metal-based oxidation to lower potential. © 2013 Elsevier Ltd. All rights reserved.

Funding

We thank the Swiss National Science Foundation and the University of Basel for financial support.

History

School

  • Science

Department

  • Chemistry

Published in

Polyhedron

Volume

64

Pages

38 - 44

Citation

CONSTABLE, E.C. ...et al., 2013. Investigating the effects of supramolecularly caging ligands in [Ru(bpy)2L]2+ complexes complexes. Polyhedron, 64, pp. 38-44.

Publisher

© Elsevier

Version

  • VoR (Version of Record)

Publisher statement

This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/

Publication date

2013

Notes

This paper is in closed access.

ISSN

0277-5387

Language

  • en