Rationalization of the unusual electrochemical behavior observed in lariat ethers and other reducible macrocyclic systems

Steven R. Miller, Deborah A. Gustowski, Zhi Hong Chen, George W. Gokel, Luis Echegoyen, Angel Kaifer

Research output: Contribution to journalArticle

190 Citations (Scopus)

Abstract

Upon the addition of cations, the observed electrochemical behavior of crown ether compounds containing or bearing reducible functions sometimes exhibits two waves or sometimes a single wave that is shifted in position relative to the original redox couple. The type of electrochemical behavior observed depends upon the binding (stability) constant (KS) for the neutral ligand-cation interaction and the binding constant (KSE) for the reduced ligand-cation interaction. A computer-based, digital simulation scheme has been devised that leads one to the conclusion that two distinct waves will be observed only when the initial cation binding constant is large and that a shifted wave will result from weaker cation-macrocycle interactions. Of special significance is the fact that the cation binding enhancement (KSE/KS) calculated from the E° values measured from the two distinct waves will generally be in error for cases in which KS for the neutral ligand-cation interaction falls in the range 1-104. For ligands in this binding range, the digital simulation procedures reported here appear to be particularly useful for the analysis of the voltammetric data.

Original languageEnglish
Pages (from-to)2021-2024
Number of pages4
JournalAnalytical Chemistry
Volume60
Issue number19
StatePublished - Dec 1 1988

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Ethers
Cations
Ligands
Bearings (structural)
Crown Ethers

ASJC Scopus subject areas

  • Analytical Chemistry

Cite this

Miller, S. R., Gustowski, D. A., Chen, Z. H., Gokel, G. W., Echegoyen, L., & Kaifer, A. (1988). Rationalization of the unusual electrochemical behavior observed in lariat ethers and other reducible macrocyclic systems. Analytical Chemistry, 60(19), 2021-2024.

Rationalization of the unusual electrochemical behavior observed in lariat ethers and other reducible macrocyclic systems. / Miller, Steven R.; Gustowski, Deborah A.; Chen, Zhi Hong; Gokel, George W.; Echegoyen, Luis; Kaifer, Angel.

In: Analytical Chemistry, Vol. 60, No. 19, 01.12.1988, p. 2021-2024.

Research output: Contribution to journalArticle

Miller, SR, Gustowski, DA, Chen, ZH, Gokel, GW, Echegoyen, L & Kaifer, A 1988, 'Rationalization of the unusual electrochemical behavior observed in lariat ethers and other reducible macrocyclic systems', Analytical Chemistry, vol. 60, no. 19, pp. 2021-2024.
Miller, Steven R. ; Gustowski, Deborah A. ; Chen, Zhi Hong ; Gokel, George W. ; Echegoyen, Luis ; Kaifer, Angel. / Rationalization of the unusual electrochemical behavior observed in lariat ethers and other reducible macrocyclic systems. In: Analytical Chemistry. 1988 ; Vol. 60, No. 19. pp. 2021-2024.
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