Unexpected Direct Synthesis of Tunable Redox-Active Benzil-Linked Polymers via the Benzoin Reaction

12 September 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


New strategies for the sustainable synthesis of redox-active organic polymers could lead to next-generation organic electrode materials for electrochemical energy storage, electrocatalysis, and electro-swing chemical separations. Among redox-active moieties, benzils or aromatic 1,2-diones are particularly attractive due to their high theoretical gravimetric capacities and fast charge/discharge rates. Herein, we demonstrate that the cyanide-catalyzed polymerization of simple dialdehyde mon-omers unexpectedly leads to insoluble redox-active benzil-linked polymers instead of the expected benzoin polymers, as confirmed by solid-state nuclear magnetic resonance spectroscopy and electrochemical characterization. Mechanistic stud-ies suggest that cyanide-mediated benzoin oxidation occurs by hydride transfer to the solvent, and that the insolubility of the benzil-linked polymers protects them from subsequent cyanolysis. The thiophene-based polymer poly(BTDA) is an in-triguing organic electrode material that demonstrates two reversible one-electron reductions with monovalent cations such as Li+ and Na+ but one two-electron reduction with divalent Mg2+. Furthermore, in lithium metal half cells, poly(BTDA) pos-seses an experimental capacity of 106 mAh/g and promising rate capabilities (64% capacity retention when the discharge rate is increased from 0.1 to 10 A/g). As such, the tandem benzoin-oxidation polymerization reported herein represents a sustainable method for the synthesis of highly tunable and redox-active organic materials.



Supplementary materials

Supporting Information
Details of all experimental procedures


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