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 journalArticlepeer-review

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

Keywords

  • Electropolymerization
  • Film
  • Mechanism
  • Phenanthroline
  • Ruthenium

ASJC Scopus subject areas

  • Analytical Chemistry
  • Chemical Engineering(all)
  • Electrochemistry

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