Anion-dominated Redox Reaction of a SAM of an Alkylthiolated Viologen Bearing a Covalently-attached Intramolecular Sulfonate Group on a Gold Electrode (Supporting Information)
The redox processes of the self-assembled monolayers (SAMs) of alkylthiolated viologens on Au electrodes are largely determined by oxidation-state-dependent binding of electrolyte anions to the viologen moiety in an aqueous solution. In this paper, we give an answer to a question: what if the SAM-forming molecule has a covalently-attached intermolecular anionic site? We used the results of the voltammetric measurements for a SAM of a viologen with a covalently-attached sulfonate group, 1-(10-mercaptodecyl)-1′-(3-sulfonatopropyl)-4,4′-bipyridinium bromide (HS-C10-V-C3-SO3− bromide salt), and examined the effect of intramolecular ion binding on the redox behavior. We found the coexistence of two distinct types of redox couples: one with a viologen moiety, which binds always to the sulfonate group, and the other with a moiety, which catches and releases an electrolyte anion from the solution upon redox. We deciphered rather complicated behavior and discussed the implications.
Actuation of Smart Gel Directionally Crawling on an Electrode Surface by Biomimetic Mechanisms
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