Surface confinement and its effects on the luminescence quenching of a ruthenium-containing metallopolymer
Dennany, Lynn and Keyes, Tia E. and Forster, Robert J. (2008) Surface confinement and its effects on the luminescence quenching of a ruthenium-containing metallopolymer. Analyst, 133 (6). pp. 753-759. ISSN 0003-2654 (https://doi.org/10.1039/b718505g)
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Luminescence quenching of the metallopolymers [Ru(bpy)(2)(PVP)(10)](2+) and [Ru(bpy)(2)(PVP)(10)Os(bpy)(2)](4+), both in solution and as thin films, is reported, where bpy is 2,2'- bipyridyl and PVP is poly(4-vinylpyridine). When the metallopolymer is dissolved in ethanol, quenching of the ruthenium excited state, Ru2+*, within [Ru(bpy)(2)(PVP)(10)](2+) by [Os(bpy)(3)](2+) proceeds by a dynamic quenching mechanism and the rate constant is (1.1 +/- 0.1) x 10(11) M-1 s(-1). This quenching rate is nearly two orders of magnitude larger than that found for quenching of monomeric [Ru(bpy)(3)](2+) under the same conditions. This observation is interpreted in terms of an energy transfer quenching mechanism in which the high local concentration of ruthenium luminophores leads to a single [Os(bpy)(3)](2+) centre quenching the emission of several ruthenium luminophores. Amplifications of this kind will lead to the development of more sensitive sensors based on emission quenching. Quenching by both [Os(bpy)(3)](2+) and molecular oxygen is significantly reduced within a thin film of the metallopolymer. Significantly, in both optically driven emission and electrogenerated chemiluminescence, emission is observed from both ruthenium and osmium centres within [Ru(bpy)(2)(PVP)(10)Os(bpy)(2)](4+) films, i.e. the ruthenium emission is not quenched by the coordinated [Os(bpy)(2)](2+) units. This observation opens up new possibilities in multi-analyte sensing since each luminophore can be used to detect separate analytes, e. g. guanine and oxoguanine.
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Item type: Article ID code: 34049 Dates: DateEvent2008PublishedSubjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 20 Oct 2011 12:35 Last modified: 25 Apr 2024 11:40 URI: https://strathprints.strath.ac.uk/id/eprint/34049