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Title: Investigating the effects of supramolecularly caging ligands in [Ru(bpy)2L]2+ complexes
Authors: Constable, Edwin C.
Housecroft, Catherine E.
Kopecky, Peter
Martin, Colin J.
Wright, Iain A.
Zampese, Jennifer A.
Keywords: Ruthenium(II)
Crystal structure
Absorption spectroscopy
Issue Date: 2013
Publisher: © Elsevier
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.
Abstract: 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.
Description: This paper is in closed access.
Sponsor: We thank the Swiss National Science Foundation and the University of Basel for financial support.
Version: Published
DOI: 10.1016/j.poly.2013.01.059
URI: https://dspace.lboro.ac.uk/2134/25415
Publisher Link: http://dx.doi.org/10.1016/j.poly.2013.01.059
ISSN: 0277-5387
Appears in Collections:Closed Access (Chemistry)

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