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Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2'-bipyridine)ruthenium(II) complexes

Barbante, Gregory J., Hogan, Conor F., Wilson, David J. D., Lewcenko, Naomi A., Pfeffer, Frederick M., Barnett, Neil W. and Francis, Paul S. 2011, Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2'-bipyridine)ruthenium(II) complexes, Analyst, vol. 136, no. 7, pp. 1329-1338.

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Title Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2'-bipyridine)ruthenium(II) complexes
Author(s) Barbante, Gregory J.
Hogan, Conor F.
Wilson, David J. D.
Lewcenko, Naomi A.
Pfeffer, Frederick M.
Barnett, Neil W.
Francis, Paul S.
Journal name Analyst
Volume number 136
Issue number 7
Start page 1329
End page 1338
Total pages 10
Publisher Royal Society of Chemistry
Place of publication Cambridge, United Kingdom
Publication date 2011
ISSN 0003-2654
1364-5528
Summary Using a combination of electrochemical, spectroscopic and computational techniques, we have explored the fundamental properties of a series of ruthenium diimine complexes designed for coupling with other molecules or surfaces for electrochemiluminescence (ECL) sensing applications. With appropriate choice of ligand functionality, it is possible to manipulate emission wavelengths while keeping the redox ability of the complex relatively constant. DFT calculations show that in the case of electron withdrawing substituents such as ester or amide, the excited state is located on the substituted bipyridine ligand whereas in the case of alkyl functionality it is localised on a bipyridine. The factors that dictate annihilation ECL efficiency are interrelated. For example, the same factors that determine ΔG for the annihilation reaction (i.e. the relative energies of the HOMO and LUMO) have a corresponding effect on the energy of the excited state product. As a result, most of the complexes populate the excited state with an efficiency (Φex) of close to 80% despite the relatively wide range of emission maxima. The quantum yield of emission (Φp) and the possibility of competing side reactions are found to be the main determinants of ECL intensity.
Language eng
Field of Research 030101 Analytical Spectrometry
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
Copyright notice ©2011, Royal Society of Chemistry
Persistent URL http://hdl.handle.net/10536/DRO/DU:30040489

Document type: Journal Article
Collections: School of Life and Environmental Sciences
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Every reasonable effort has been made to ensure that permission has been obtained for items included in DRO. If you believe that your rights have been infringed by this repository, please contact drosupport@deakin.edu.au.