Kerr Emily, Doeven Egan H, Barbante Gregory J, Hogan Conor F, Bower David J, Donnelly Paul S, Connell Timothy U, Francis Paul S
Centre for Chemistry and Biotechnology , School of Life and Environmental Sciences , Faculty of Science , Engineering and Built Environment , Deakin University , Geelong , Victoria 3220 , Australia . Email:
Department of Chemistry , La Trobe Institute for Molecular Science , La Trobe University , Melbourne , Victoria 3086 , Australia . Email:
Chem Sci. 2015 Jan 1;6(1):472-479. doi: 10.1039/c4sc02697g. Epub 2014 Oct 15.
We demonstrate the mixed annihilation electrogenerated chemiluminescence of tris(2,2'-bipyridine)ruthenium(ii) with various cyclometalated iridium(iii) chelates. Compared to mixed ECL systems comprising organic luminophores, the absence of T-route pathways enables effective predictions of the observed ECL based on simple estimations of the exergonicity of the reactions leading to excited state production. Moreover, the multiple, closely spaced reductions and oxidations of the metal chelates provide the ability to finely tune the energetics and therefore the observed emission colour. Distinct emissions from multiple luminophores in the same solution are observed in numerous systems. The relative intensity of these emissions and the overall emission colour are dependent on the particular oxidized and reduced species selected by the applied electrochemical potentials. Finally, these studies offer insights into the importance of electronic factors in the question of whether the reduced or oxidized partner becomes excited in annihilation ECL.
我们展示了三（2,2'-联吡啶）钌（II）与各种环金属化铱（III）螯合物的混合湮灭电化学发光。与包含有机发光体的混合电化学发光系统相比，不存在T-途径使得能够基于对导致激发态产生的反应的放能性的简单估计，对观察到的电化学发光进行有效预测。此外，金属螯合物的多个紧密间隔的还原和氧化提供了精细调节能量学的能力，从而调节观察到的发射颜色。在许多系统中都观察到同一溶液中多个发光体的不同发射。这些发射的相对强度和整体发射颜色取决于所施加的电化学电位所选择的特定氧化态和还原态物种。最后，这些研究深入了解了电子因素在湮灭电化学发光中还原或氧化伙伴是否被激发这一问题中的重要性。
