Surface confinement and its effects on the luminescence quenching of a ruthenium-containing metallopolymer

Lynn Dennany, Tia E. Keyes, Robert J. Forster

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)753-759
Number of pages7
JournalAnalyst
Volume133
Issue number6
DOIs
Publication statusPublished - 2008

Fingerprint

ruthenium
Ruthenium
luminescence
Luminescence
Quenching
Osmium
osmium
2,2'-Dipyridyl
Energy Transfer
Guanine
ethanol
amplification
Ethanol
bis(bipyridyl)ruthenium(II)
effect
Thin films
Oxygen
sensor
Chemiluminescence
Molecular oxygen

Keywords

  • electron-transfer
  • direct electrochemiluminescence
  • artificial photosynthesis
  • ultrathin films
  • energy-transfer
  • dna
  • complexes

Cite this

Dennany, Lynn ; Keyes, Tia E. ; Forster, Robert J. / Surface confinement and its effects on the luminescence quenching of a ruthenium-containing metallopolymer. In: Analyst. 2008 ; Vol. 133, No. 6. pp. 753-759.
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abstract = "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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Surface confinement and its effects on the luminescence quenching of a ruthenium-containing metallopolymer. / Dennany, Lynn; Keyes, Tia E.; Forster, Robert J.

In: Analyst, Vol. 133, No. 6, 2008, p. 753-759.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Surface confinement and its effects on the luminescence quenching of a ruthenium-containing metallopolymer

AU - Dennany, Lynn

AU - Keyes, Tia E.

AU - Forster, Robert J.

PY - 2008

Y1 - 2008

N2 - 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.

AB - 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.

KW - electron-transfer

KW - direct electrochemiluminescence

KW - artificial photosynthesis

KW - ultrathin films

KW - energy-transfer

KW - dna

KW - complexes

U2 - 10.1039/b718505g

DO - 10.1039/b718505g

M3 - Article

VL - 133

SP - 753

EP - 759

JO - Analyst

JF - Analyst

SN - 0003-2654

IS - 6

ER -