Electrochemical Properties of a Pyridine-Tunable Trisferrocenylborane

ORGANOMETALLICS(2024)

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Abstract
Non-aqueous redox flow batteries (NARFBs) offer promising solutions for sustainable and long-term energy storage. Herein, trisferrocenylborane (BFc(3); Fc = ferrocene, Cp2Fe, and Cp = C5H5-) is examined for its potential role as a tunable anolyte for use in NARFBs. BFc(3) contains three readily oxidized ferrocene units along with a mediating borane that hosts an empty p orbital, allowing tuned access to specific redox properties as a function of nucleophile choice. The electrochemical behavior (cyclic voltammetry, charging/discharging cycles, etc.) of BFc(3) are accordingly examined in the presence of a series of 4-R-substituted pyridines (R = NMe2, NH2, Bu-t, Et, or I), with a range of nitrogen donor strengths. These adducts produce a linear correlation that relates E-1/2 to the para-substituent constant (sigma(p)), showing a tunability of 200-300 mV based on donor choice alone; solvent effects using tetrahydrofuran, acetonitrile, and dichloromethane are additionally discussed.
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