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

The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures
The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures
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:L-2 and M:L-3 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 self-assemblies 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.
1478-6524
457-471
Kotova, Oxana
cc7a22e9-8aab-40b0-ac86-115e48bea549
Blasco, Salvador
2124f7c5-3285-4f6d-934a-ced2c607426b
Twamley, Brendan
f8428d8a-a1bd-4696-a48a-3386fd2ccda6
O'Brien, John
0906821d-4431-47e6-8155-27de5d7f9612
Peacock, Robert D.
cf938797-c8b4-43f6-b49d-6af680d03e3c
Kitchen, Jonathan
3999f5cb-d53e-4c51-b750-627bd2a1b9b6
Martínez-Calvo, Miguel
30469ce8-2b95-4bb4-9c48-d39c1038c411
Gunnlaugsson, Thorfinnur
bbfcaaa6-2aca-47c9-9b7b-954442218f50
Kotova, Oxana
cc7a22e9-8aab-40b0-ac86-115e48bea549
Blasco, Salvador
2124f7c5-3285-4f6d-934a-ced2c607426b
Twamley, Brendan
f8428d8a-a1bd-4696-a48a-3386fd2ccda6
O'Brien, John
0906821d-4431-47e6-8155-27de5d7f9612
Peacock, Robert D.
cf938797-c8b4-43f6-b49d-6af680d03e3c
Kitchen, Jonathan
3999f5cb-d53e-4c51-b750-627bd2a1b9b6
Martínez-Calvo, Miguel
30469ce8-2b95-4bb4-9c48-d39c1038c411
Gunnlaugsson, Thorfinnur
bbfcaaa6-2aca-47c9-9b7b-954442218f50

Kotova, Oxana, Blasco, Salvador, Twamley, Brendan, O'Brien, John, Peacock, Robert D., Kitchen, Jonathan, Martínez-Calvo, Miguel and Gunnlaugsson, Thorfinnur (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), 457-471. (doi:10.1039/c4sc02474e).

Record type: Article

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:L-2 and M:L-3 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 self-assemblies 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.

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Accepted/In Press date: 10 October 2014
e-pub ahead of print date: 10 October 2014
Published date: 2015
Organisations: Organic Chemistry: SCF

Identifiers

Local EPrints ID: 395544
URI: http://eprints.soton.ac.uk/id/eprint/395544
ISSN: 1478-6524
PURE UUID: e96715be-5ec3-44b6-8478-45b39d782f70
ORCID for Jonathan Kitchen: ORCID iD orcid.org/0000-0002-7139-5666

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Date deposited: 31 May 2016 15:51
Last modified: 15 Mar 2024 00:42

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Contributors

Author: Oxana Kotova
Author: Salvador Blasco
Author: Brendan Twamley
Author: John O'Brien
Author: Robert D. Peacock
Author: Jonathan Kitchen ORCID iD
Author: Miguel Martínez-Calvo
Author: Thorfinnur Gunnlaugsson

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