Luminescent metal complexes within polyelectrolyte layers: tuning electron and energy transfer

Lynn Dennany, Gordon G. Wallace, Robert J. Forster

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The electrochemical and photophysical properties or a luminescent metal center, [Os(bPY)(3)](2+), are significantly modified by encapsulation within a conducting polymer composite film. Cyclic voltammetry reveals that the encapsulation in an inherently conducting polymer, polyaniline (Pani) or polypyrrole (PPy), can dramatically influence the charge-transfer rates between the metal centers. The increased electron transport, most likely mediated through the conducting polymer backbone, significantly enhances the electrochemiluminescence (ECL) efficiency. The increased communication between adjacent metal centers can also result in other interesting properties, such as photoinduced electron-transfer processes. In situ electron spin resonance (ESR) spectroscopy has been used to probe the photooxidation of an osmium metal center encapsulated in a PPy composite film. The irradiation of PPy in the presence of the osmium metal center resulted in the photo-oxidation of the Os2+ to Os3+ state and the consequent reduction of the PPy polyelectrolyte. The degree of communication between luminescent metal centers allows the composite properties to be tuned for various applications including ECL sensor devices and light-switching and light-harvesting systems.

LanguageEnglish
Pages14053-14060
Number of pages8
JournalLangmuir
Volume25
Issue number24
DOIs
Publication statusPublished - 15 Dec 2009

Fingerprint

Coordination Complexes
Metal complexes
Polyelectrolytes
Energy transfer
electron transfer
Tuning
Metals
energy transfer
tuning
polypyrroles
Polypyrroles
Electrons
Conducting polymers
conducting polymers
metals
Osmium
Photooxidation
osmium
photooxidation
Composite films

Keywords

  • ruthenium-containing metallopolymers
  • electrogenerated chemiluminescence
  • direct elecrochemiluminescence
  • supporting electrolyte
  • conducting polymers
  • ultrathin films
  • redox polymers
  • composite film

Cite this

Dennany, Lynn ; Wallace, Gordon G. ; Forster, Robert J. / Luminescent metal complexes within polyelectrolyte layers: tuning electron and energy transfer. In: Langmuir. 2009 ; Vol. 25, No. 24. pp. 14053-14060.
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Luminescent metal complexes within polyelectrolyte layers: tuning electron and energy transfer. / Dennany, Lynn; Wallace, Gordon G.; Forster, Robert J.

In: Langmuir, Vol. 25, No. 24, 15.12.2009, p. 14053-14060.

Research output: Contribution to journalArticle

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T1 - Luminescent metal complexes within polyelectrolyte layers: tuning electron and energy transfer

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AB - The electrochemical and photophysical properties or a luminescent metal center, [Os(bPY)(3)](2+), are significantly modified by encapsulation within a conducting polymer composite film. Cyclic voltammetry reveals that the encapsulation in an inherently conducting polymer, polyaniline (Pani) or polypyrrole (PPy), can dramatically influence the charge-transfer rates between the metal centers. The increased electron transport, most likely mediated through the conducting polymer backbone, significantly enhances the electrochemiluminescence (ECL) efficiency. The increased communication between adjacent metal centers can also result in other interesting properties, such as photoinduced electron-transfer processes. In situ electron spin resonance (ESR) spectroscopy has been used to probe the photooxidation of an osmium metal center encapsulated in a PPy composite film. The irradiation of PPy in the presence of the osmium metal center resulted in the photo-oxidation of the Os2+ to Os3+ state and the consequent reduction of the PPy polyelectrolyte. The degree of communication between luminescent metal centers allows the composite properties to be tuned for various applications including ECL sensor devices and light-switching and light-harvesting systems.

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