Unexpected Direct Synthesis of Tunable Redox-Active Benzil-Linked Polymers via the Benzoin Reaction.
Unexpected Direct Synthesis of Tunable Redox-Active Benzil-Linked Polymers via the Benzoin Reaction.
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DOI：
10.1021/acsapm.2c02047
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发表时间：
2022-12
影响因子：
5
通讯作者：
Christina Cong;Jaehwan Kim;Cara N. Gannett;H. Abruña;P. Milner
中科院分区：
文献类型：
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作者：
Christina Cong;Jaehwan Kim;Cara N. Gannett;H. Abruña;P. Milner
可持续合成氧化还原活性有机聚合物的策略可能导致用于电化学储能，电催化和电摆动化学分离的下一代有机电极材料。在氧化还原活性基团中，苯基化合物或芳香族1,2-二酮因其较高的理论重量容量和快速的充放电速率而特别具有吸引力。在此，我们证明了氰化物催化的简单双醛单体聚合意外地导致了不溶性的氧化还原活性苯连接聚合物，而不是预期的苯甲酸聚合物，正如固态核磁共振波谱和电化学表征所支持的那样。机理研究表明，氰化物介导的苯甲酸氧化是通过氢化物转移到溶剂中发生的，而苯连接聚合物的不溶解性保护它们免受随后的氰化反应。噻吩基聚合物聚（BTDA）是一种有趣的有机电极材料，它与Li+和Na+等一价阳离子有两个可逆的单电子还原，与二价Mg2+有一个双电子还原。因此，本文报道的串联苯甲酰胺氧化聚合代表了一种合成高度可调和氧化还原活性有机材料的可持续方法。
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 monomers unexpectedly leads to insoluble redox-active benzil-linked polymers instead of the expected benzoin polymers, as supported by solid-state nuclear magnetic resonance spectroscopy and electrochemical characterization. Mechanistic studies 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 intriguing 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+. As such, the tandem benzoin-oxidation polymerization reported herein represents a sustainable method for the synthesis of highly tunable and redox-active organic materials.