Synthesis, cyclic voltammetric studies, and electrogenerated chemiluminescence of a new donor - Acceptor molecule: 3,7-[bis[4-phenyl-2-quinolyl]]-10-methylphenothiazine

R. Y. Lai, E. F. Fabrizio, L. Lu, S. A. Jenekhe, A. J. Bard

Research output: Contribution to journalArticle

149 Citations (Scopus)

Abstract

We report here the synthesis of a novel compound that contains two electron-accepting phenylquinoline groups covalently attached to the 3,7-positions of a light-emitting electron donor, 10-methylphenothiazine. The optimized geometry as determined from semiempirical MNDO calculations shows that the phenylquinoline moieties are twisted ∼77.5° from the phenothiazine central ring. As a result, no molecular orbital overlap between these two groups exists, inhibiting any delocalization of the charge upon electrochemical oxidation or reduction. Comparison between cyclic voltammograms obtained of this compound as well as of the individual compounds, 10-methylphenothiazine and 2-phenylquinonine, did indeed show no change in the electrochemical behavior of these two groups upon the covalent attachment, confirming the results obtained from the semiempirical calculations. A shift to lower energy wavelengths of phenothiazine was observed upon the addition of the electron-deficient phenylquinoline moieties. Overall, this unique geometry allows us to electrochemically produce the stable radical ions needed to generate the light-emitting excited state of phenothiazine within a potential window not obtainable with just 10-methylphenothiazine. ECL spectrum produced by annihilation between the radical cation of phenothiazine and the radical anion of phenylquinoline shows good agreement with the fluorescence emission of 10-methylphenothiazine.

Original languageEnglish (US)
Pages (from-to)9112-9118
Number of pages7
JournalJournal of the American Chemical Society
Volume123
Issue number37
DOIs
StatePublished - Sep 19 2001

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Chemiluminescence
Luminescence
Molecules
Electrons
Emitter coupled logic circuits
Geometry
Electrochemical oxidation
Molecular orbitals
Light
Excited states
Negative ions
Positive ions
Fluorescence
Anions
Cations
Wavelength
Ions
N-methylphenothiazine
phenothiazine

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Synthesis, cyclic voltammetric studies, and electrogenerated chemiluminescence of a new donor - Acceptor molecule : 3,7-[bis[4-phenyl-2-quinolyl]]-10-methylphenothiazine. / Lai, R. Y.; Fabrizio, E. F.; Lu, L.; Jenekhe, S. A.; Bard, A. J.

In: Journal of the American Chemical Society, Vol. 123, No. 37, 19.09.2001, p. 9112-9118.

Research output: Contribution to journalArticle

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abstract = "We report here the synthesis of a novel compound that contains two electron-accepting phenylquinoline groups covalently attached to the 3,7-positions of a light-emitting electron donor, 10-methylphenothiazine. The optimized geometry as determined from semiempirical MNDO calculations shows that the phenylquinoline moieties are twisted ∼77.5° from the phenothiazine central ring. As a result, no molecular orbital overlap between these two groups exists, inhibiting any delocalization of the charge upon electrochemical oxidation or reduction. Comparison between cyclic voltammograms obtained of this compound as well as of the individual compounds, 10-methylphenothiazine and 2-phenylquinonine, did indeed show no change in the electrochemical behavior of these two groups upon the covalent attachment, confirming the results obtained from the semiempirical calculations. A shift to lower energy wavelengths of phenothiazine was observed upon the addition of the electron-deficient phenylquinoline moieties. Overall, this unique geometry allows us to electrochemically produce the stable radical ions needed to generate the light-emitting excited state of phenothiazine within a potential window not obtainable with just 10-methylphenothiazine. ECL spectrum produced by annihilation between the radical cation of phenothiazine and the radical anion of phenylquinoline shows good agreement with the fluorescence emission of 10-methylphenothiazine.",
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