Abstract
Here, we investigate the electrochemical properties and stability of 1,1'-ferrocene-bisphosphonates in aqueous solutions. 31P NMR spectroscopy enables to track decomposition at extreme pH conditions revealing partial disintegration of the ferrocene core in air and under an argon atmosphere. ESI-MS indicates the decomposition pathways to be different in aqueous H3PO4, phosphate buffer, or NaOH solutions. Cyclovoltammetry exhibits completely reversible redox chemistry of the evaluated bisphosphonates, sodium 1,1'-ferrocene-bis(phosphonate) (3) and sodium 1,1'-ferrocene-bis(methylphosphonate) (8), from pH 1.2 to pH 13. Both the compounds feature freely diffusing species as determined using the Randles-Sevcik analysis. The activation barriers determined by rotating disk electrode measurements revealed asymmetry for oxidation and reduction. The compounds are tested in a hybrid flow battery using anthraquinone-2-sulfonate as the counterside, yielding only moderate performance.
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