Modulation of Quinone PCET Reaction by Ca2+ Ion Captured by Calix[4]quinone in Water

By Kim, Yang-Rae; Kim, R. Soyoung; Kang, Sun Kil; Choi, Myung Gil; Kim, Hong Yeong; Cho, Daeheum; Lee, Jin Yong; Chang, Suk-Kyu & Chung, Taek Dong
Published in Journal of the American Chemical Society NULL 2013

Abstract

Calix[4]arene-triacid-monoquinone (CTAQ), a quinone-containing water-soluble ionophore, was utilized to investigate how proton-coupled electron transfer (PCET) reactions of quinones were influenced by redox-inactive metal ions in aqueous environment. This ionophoric quinone derivative captured a Ca2+ ion that drastically altered the voltammetric behavior of quinone, showing a characteristic response to pH and unique redox wave separation. Spectroelectrochemistry verified significant stabilization of the semiquinone, and electrocatalytic currents were observed in the presence of Ca2+-free CTAQ. Using digital simulation of cyclic voltammograms to clarify how the thermodynamic properties of quinones were altered, a simple scheme was proposed that successfully accounted for all the observations. The change induced by Ca2+ complexation was explained on the basis of the combined effects of the electrostatic influence of the captured metal ion and hydrogen bonding of water molecules with the support of DFT calculation.

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