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New perspectives on the annihilation electrogenerated chemiluminescence of mixed metal complexes in solution1

Kerr, Emily et al.

Chemical science. Volume 7:Issue 8 (2016); pp 5271-5279 -- Royal Society of Chemistry

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  • Title:
    New perspectives on the annihilation electrogenerated chemiluminescence of mixed metal complexes in solution1
  • Author: Kerr, Emily;
    Doeven, Egan H.;
    Barbante, Gregory J.;
    Hogan, Conor F.;
    Hayne, David J.;
    Donnelly, Paul S.;
    Francis, Paul S.
  • Found In: Chemical science. Volume 7:Issue 8 (2016); pp 5271-5279
  • Journal Title: Chemical science
  • Subjects: Chemistry--Periodicals; Dewey: 540.5
  • Rights: legaldeposit
  • Publication Details: Royal Society of Chemistry
  • Abstract: Abstract :

    We examine energy transfer and quenching within annihilation ECL systems comprising mixed metal-complexes in solution, and show the dependence of the emission intensities on luminophore concentration and the applied potentials.

    Abstract :

    Preliminary explorations of the annihilation electrogenerated chemiluminescence (ECL) of mixed metal complexes have revealed opportunities to enhance emission intensities and control the relative intensities from multiple luminophores through the applied potentials. However, the mechanisms of these systems are only poorly understood. Herein, we present a comprehensive characterisation of the annihilation ECL of mixtures of tris(2, 2′-bipyridine)ruthenium(ii) hexafluorophosphate ([Ru(bpy)3](PF6)2) and fac -tris(2-phenylpyridine)iridium(iii) ([Ir(ppy)3]). This includes a detailed investigation of the change in emission intensity from each luminophore as a function of both the applied electrochemical potentials and the relative concentrations of the two complexes, and a direct comparison with two mixed (Ru/Ir) ECL systems for which emission from only the ruthenium-complex was previously reported. Concomitant emission from both luminophores was observed in all three systems, but only when: (1) the applied potentials were sufficient to generate the intermediates required to form the electronically excited state of both complexes; and (2) the concentration of the iridium complex (relative to the ruthenium complex) was sufficient to overcome quenching processes. Both enhancement and quenching of the ECL of the ruthenium complex was observed, depending on the experimental conditions. The observations were rationalised through several complementary mechanisms, including resonance energy transfer and various energetically favourable electron-transfer pathways.


  • Identifier: System Number: LDEAvdc_100052648793.0x000001; Journal ISSN: 2041-6520; 10.1039/c6sc01570k
  • Publication Date: 2016
  • Physical Description: Electronic
  • Shelfmark(s): ELD Digital store

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