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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 20, Number 2
BKCSDE 20(2)
February 20, 1999 

Electrochemical Behavior of Viologens with Long Alkyl Chains Depending on Their Concentrations and the Concentration of Micelles and Cyclodextrins
Youngmi Lee, Chongmok Lee
The concentration dependence of the electrochemical behaviors of 1-methyl-1'-alkyl-4,4'-bipyridinium chloride (ClCnV2+: n = 14, 16, 18) was investigated using cyclic voltammetric, chronocoulometric and spectroelectrochemical techniques. The electrochemical behavior was investigated in terms of critical micelle concentrations (CMCs) of C1CnV2+ determined by spectroscopic methods. The voltammetric behavior of these three surfactant viologens at lower and higher concentrations than their CMC varied: the relieved adsorption/precipitation of 1-e- reduction product was observed for ClC14V2+ with an increase in its concentration, whereas reorientation after adsorption/precipitation resulted in two anodic peak responses for C1C16V+ and C1C18V+. These phenomena were interpreted as the competition between electrodeposition and dissolution into the micelle. This was supported by the incorporation of C1C14V+ into cetyltrimethylammonium bromide (CTAB) micelle despite their electrostatic repulsion. Stabilization of the viologen cation radical (V+) by cyclodextrins (CDs) was also observed, where (α-CD and methylated β-CD were more effective than β-CD in suppression of adsorption/dimerization of viologens having a long alkyl chain.
187 - 194
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