Characterization of exciplexes generated by excited tris-diimine-ruthenium(II) complexes and silver(I) ion of ground state

L. Fodor, Attila Horváth

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Abstract

Luminescent bimolecular and termolecular exciplexes of *[Ru(bpy)3]2+ and *[Ru(phen)3]2+ (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) formed by silver ions have been characterized and compared. Formation constants, luminescence lifetime, radiative and non-radiative decay constants were determined at room temperature. Oxidative quenching measurements in the [Ru (bpy)3]2+-Ag+ system using MV2+ (MV2+ = 1,1′-dimethyl-4,4′-bipyridinium) as an electron acceptor resulted in quenching rate constants, (3.1±0.2) × 109, (3.1±0.3) × 109, (1.6±0.3) × 109 and cage escape efficiencies, 0.11±0.01, 0.05±0.01, 0.06±0.01, for *[Ru(bpy)3]2+, *[Ru(bpy)3] Ag3+ and *[Ru(bpy)3] Ag2 4+, respectively. Temperature-dependent luminescence lifetime measurements in aqueous solutions revealed that the exciplex formation causes a considerable change in the deactivation pathways of the excited species. Exciplex formation results in a decrease in the efficiency of the thermally activated decay through MLCT→dd transition and in an increase of the efficiency of deactivation to the ground state via other non radiative processes. The thermodynamic parameters of the exciplex formation have been estimated.

Original languageEnglish
Pages (from-to)213-223
Number of pages11
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume112
Issue number2-3
Publication statusPublished - Jan 31 1998

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Ruthenium
Silver
Ground state
ruthenium
silver
Ions
ground state
Luminescence
Quenching
deactivation
ions
quenching
luminescence
Rate constants
decay
radiative lifetime
Thermodynamics
escape
Temperature
Electrons

Keywords

  • Exciplex
  • Luminescence dynamics
  • Photophysics
  • Quenching

ASJC Scopus subject areas

  • Bioengineering
  • Physical and Theoretical Chemistry

Cite this

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title = "Characterization of exciplexes generated by excited tris-diimine-ruthenium(II) complexes and silver(I) ion of ground state",
abstract = "Luminescent bimolecular and termolecular exciplexes of *[Ru(bpy)3]2+ and *[Ru(phen)3]2+ (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) formed by silver ions have been characterized and compared. Formation constants, luminescence lifetime, radiative and non-radiative decay constants were determined at room temperature. Oxidative quenching measurements in the [Ru (bpy)3]2+-Ag+ system using MV2+ (MV2+ = 1,1′-dimethyl-4,4′-bipyridinium) as an electron acceptor resulted in quenching rate constants, (3.1±0.2) × 109, (3.1±0.3) × 109, (1.6±0.3) × 109 and cage escape efficiencies, 0.11±0.01, 0.05±0.01, 0.06±0.01, for *[Ru(bpy)3]2+, *[Ru(bpy)3] Ag3+ and *[Ru(bpy)3] Ag2 4+, respectively. Temperature-dependent luminescence lifetime measurements in aqueous solutions revealed that the exciplex formation causes a considerable change in the deactivation pathways of the excited species. Exciplex formation results in a decrease in the efficiency of the thermally activated decay through MLCT→dd transition and in an increase of the efficiency of deactivation to the ground state via other non radiative processes. The thermodynamic parameters of the exciplex formation have been estimated.",
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T1 - Characterization of exciplexes generated by excited tris-diimine-ruthenium(II) complexes and silver(I) ion of ground state

AU - Fodor, L.

AU - Horváth, Attila

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N2 - Luminescent bimolecular and termolecular exciplexes of *[Ru(bpy)3]2+ and *[Ru(phen)3]2+ (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) formed by silver ions have been characterized and compared. Formation constants, luminescence lifetime, radiative and non-radiative decay constants were determined at room temperature. Oxidative quenching measurements in the [Ru (bpy)3]2+-Ag+ system using MV2+ (MV2+ = 1,1′-dimethyl-4,4′-bipyridinium) as an electron acceptor resulted in quenching rate constants, (3.1±0.2) × 109, (3.1±0.3) × 109, (1.6±0.3) × 109 and cage escape efficiencies, 0.11±0.01, 0.05±0.01, 0.06±0.01, for *[Ru(bpy)3]2+, *[Ru(bpy)3] Ag3+ and *[Ru(bpy)3] Ag2 4+, respectively. Temperature-dependent luminescence lifetime measurements in aqueous solutions revealed that the exciplex formation causes a considerable change in the deactivation pathways of the excited species. Exciplex formation results in a decrease in the efficiency of the thermally activated decay through MLCT→dd transition and in an increase of the efficiency of deactivation to the ground state via other non radiative processes. The thermodynamic parameters of the exciplex formation have been estimated.

AB - Luminescent bimolecular and termolecular exciplexes of *[Ru(bpy)3]2+ and *[Ru(phen)3]2+ (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) formed by silver ions have been characterized and compared. Formation constants, luminescence lifetime, radiative and non-radiative decay constants were determined at room temperature. Oxidative quenching measurements in the [Ru (bpy)3]2+-Ag+ system using MV2+ (MV2+ = 1,1′-dimethyl-4,4′-bipyridinium) as an electron acceptor resulted in quenching rate constants, (3.1±0.2) × 109, (3.1±0.3) × 109, (1.6±0.3) × 109 and cage escape efficiencies, 0.11±0.01, 0.05±0.01, 0.06±0.01, for *[Ru(bpy)3]2+, *[Ru(bpy)3] Ag3+ and *[Ru(bpy)3] Ag2 4+, respectively. Temperature-dependent luminescence lifetime measurements in aqueous solutions revealed that the exciplex formation causes a considerable change in the deactivation pathways of the excited species. Exciplex formation results in a decrease in the efficiency of the thermally activated decay through MLCT→dd transition and in an increase of the efficiency of deactivation to the ground state via other non radiative processes. The thermodynamic parameters of the exciplex formation have been estimated.

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