Effect of surface immobilization on the electrochemiluminescence of ruthenium-containing metallopolymers

Dennany, L and Hogan, C F and Keyes, T E and Forster, R J (2006) Effect of surface immobilization on the electrochemiluminescence of ruthenium-containing metallopolymers. Analytical Chemistry, 78 (5). pp. 1412-1417. ISSN 0003-2700 (https://doi.org/10.1021/ac0513919)

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Abstract

The effect of surface confinement on the electrochemiluminescence (ECL) properties of metallopolymer [Ru(bpy)(2)(PVP)(10)](2+), where bpy is 2,2'-bipyridyl and PVP is poly(4-vinylpyridine), is reported. Immobilizing a luminescent material on an electrode surface can substantially modulate its photophysical properties. Significantly, our study revealed that the overall efficiency of the ECL reaction for the metallopolymer film is almost four times higher, at 0.15%, than the highest value obtained for [Ru(bpy)(2)(PVP)(10)](2+) dissolved in solution, (phi(ECL) = 0.04%). Electrochemistry has been used to create well-defined concentrations of the quencher Ru3+ within the film. Analysis of both the steady-state luminescence and lifetimes of the film reveals that static quenching by electron transfer between the photoexcited Ru2+* and the Ru3+ centers is the dominant quenching mechanism. The bimolecular rate of electron transfer is (2.5 +/- 0.4) x 10(6) M-1 s(-1). The implications of these findings for ECL-based sensors, in terms of optimum luminophore loading, is considered.

ORCID iDs

Dennany, L ORCID logoORCID: https://orcid.org/0000-0002-5481-1066, Hogan, C F, Keyes, T E and Forster, R J;
CORE (COnnecting REpositories)