Frontiers in Chemistry (Jan 2021)
Redox Property Tuning in Bipyridinium Salts
Abstract
Bipyridinium salts are currently very popular due to their perspective applications in redox flow batteries. Hence, we designed and prepared a series of bipyridiniums based on 2,2′-, 3,3′-, and 4,4′-bipyridine and 2,2′-bipyrimidine. The straightforward synthesis utilizes commercially or readily available starting compounds and their direct N-alkylation, mostly using 1,3-propanesultone. All eleven target derivatives with systematically evolved structure were investigated by cyclic voltammetry, which allowed elucidating thorough structure-property relationships. The electrochemical behavior depends primarily on the parent scaffold, type of N-alkylation, number of quaternized nitrogen atoms, planarity, counter ion as well as the used media. Two derivatives featuring quasi-reversible redox processes were further tested on rotating disc electrode and in a flow battery half-cell. 4,4′-Bipyridinium derivative bearing two sultone residues showed better performance and stability in the flow half-cell with small capacity decays of 0.09/0.15% per reduction-oxidation cycle, based on the number of the utilized redox processes (one/two).
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