The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures

Kotova, O., Blasco, S., Twamley, B., O'Brien, J., Peacock, R. D., Kitchen, J. A., Martínez-Calvo, M. and Gunnlaugsson, T. (2015) The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures. Chemical Science, 6(1), pp. 457-471. (doi: 10.1039/c4sc02474e)

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Abstract

The binding of asymmetrical and optically pure tridentate ligands (L = 1(S) and 1(R)) containing one carboxylic group and 2-naphthyl as an antenna to lanthanide ions (M = La(III) and Eu(III)) was studied in CH3CN, showing the successive formation of M:L, M:L2 and M:L3 stoichiometric species in solution. The europium complexes EuL3 were also synthesised, structurally characterised and their photophysical properties probed in CH3OH and CH3CN. The changes in the chiroptical properties of both 1(S) and 1(R) were used (by circular dichroism (CD) spectroscopy) to monitor the formation of these chiral selfassemblies in solution. While circularly polarised luminescence (CPL) showed the formation of Eu(1(S))3 and Eu(1(R))3 as enantiomers, with high luminescence dissymmetry factors (glum), fitting the CD changes allowed for binding constants to be determined that were comparable to those seen in the analyses of absorbance and luminescence changes.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Peacock, Dr Robert
Authors: Kotova, O., Blasco, S., Twamley, B., O'Brien, J., Peacock, R. D., Kitchen, J. A., Martínez-Calvo, M., and Gunnlaugsson, T.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemical Science
Publisher:Royal Society of Chemistry
ISSN:2041-6520
ISSN (Online):2041-6539
Copyright Holders:Copyright © 2015 The Royal Society of Chemistry
First Published:First published in Chemical Science 6(1):457-471
Publisher Policy:Reproduced under a Creative Commons License

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