On the mechanism of oxidative electropolymerization and film formation for phenanthroline-containing complexes of ruthenium

Hai Tao Zhang, Susan G. Yan, P. Subramanian, Lisa M. Skeens-Jones, Charlotte Stern, Joseph T Hupp

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

New experiments involving electrochemistry, Auger spectroscopy and elemental analysis of films and film-forming compounds, as well as X-ray crystallography and electrochemistry of a key model compound, have been used to elucidate the linkage structure and probable mechanism of formation of oxidatively generated polymeric and copolymeric films of phenanthroline-containing complexes of ruthenium. Film formation evidently involves indirect electrochemical activation of coordinated 1,10-phenanthroline to nucleophilic attack by the non-coordinated pyridyl nitrogen of a dipyridyl ligand singly coordinated to a second metal center. The resulting linkage is comprised of a carbon/nitrogen bond with an excess positive charge residing on the nitrogen atom. Electrochemical oxidation of a complexed metal ion (typically Ru(II)) drives the polymerization by: (a) rendering the 4 site of phenanthroline significantly electrophilic, and (b) providing an oxidizing equivalent for eventual H atom elimination and pyridinium ion formation via an internal electron transfer sequence.

Original languageEnglish
Pages (from-to)23-29
Number of pages7
JournalJournal of Electroanalytical Chemistry
Volume414
Issue number1
DOIs
Publication statusPublished - Sep 26 1996

Fingerprint

Phenanthrolines
Ruthenium
Electropolymerization
Nitrogen
Electrochemistry
Atoms
Electrochemical oxidation
X ray crystallography
Metal ions
Carbon
Metals
Chemical activation
Ligands
Polymerization
Spectroscopy
Ions
Electrons
Chemical analysis
Experiments

Keywords

  • Electropolymerization
  • Film
  • Mechanism
  • Phenanthroline
  • Ruthenium

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Analytical Chemistry
  • Electrochemistry

Cite this

On the mechanism of oxidative electropolymerization and film formation for phenanthroline-containing complexes of ruthenium. / Zhang, Hai Tao; Yan, Susan G.; Subramanian, P.; Skeens-Jones, Lisa M.; Stern, Charlotte; Hupp, Joseph T.

In: Journal of Electroanalytical Chemistry, Vol. 414, No. 1, 26.09.1996, p. 23-29.

Research output: Contribution to journalArticle

Zhang, Hai Tao ; Yan, Susan G. ; Subramanian, P. ; Skeens-Jones, Lisa M. ; Stern, Charlotte ; Hupp, Joseph T. / On the mechanism of oxidative electropolymerization and film formation for phenanthroline-containing complexes of ruthenium. In: Journal of Electroanalytical Chemistry. 1996 ; Vol. 414, No. 1. pp. 23-29.
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