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 E. Kaifer

Research output: Contribution to journalArticlepeer-review

190 Scopus citations

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 (US)
Pages (from-to)2021-2024
Number of pages4
JournalAnalytical Chemistry
Volume60
Issue number19
DOIs
StatePublished - Oct 1 1988

ASJC Scopus subject areas

  • Analytical Chemistry

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