Simultaneously Enhancing the Redox Potential and Stability of Multi-Redox Organic Catholytes by Incorporating Cyclopropenium Substituents
作者:Yichao Yan、Sophia G. Robinson、Thomas P. Vaid、Matthew S. Sigman、Melanie S. Sanford
DOI:10.1021/jacs.1c07237
日期:2021.8.25
the second oxidation (which occurs at 1.20 V vs Fc/Fc+ in the phenothiazine derivative) reversible. The electron-withdrawing nature of the DAC unit is responsible for the increase in redox potential, while the DAC substituents stabilize oxidized forms of the molecules through resonance delocalization of charge and unpaired spin density. These new catholytes were deployed in two-electron redox flow
通过将二氨基环丙烯 (DAC) 取代基附加到吩嗪和吩噻嗪核,开发了用于非水氧化还原液流电池的高氧化还原电位的双电子有机阴极电解质。母体杂环在中等电位下表现出两种部分可逆的氧化[均低于 0.7 V 对二茂铁/二茂铁 (Fc/Fc + )]。DAC 取代基的加入对这些系统具有双重影响。DAC 组将两对的氧化还原电位提高了约 300 mV,同时使第二次氧化(发生在 1.20 V vs Fc/Fc +在吩噻嗪衍生物中)可逆。DAC 单元的吸电子性质导致氧化还原电位的增加,而 DAC 取代基通过电荷的共振离域和未配对的自旋密度稳定分子的氧化形式。这些新的阴极电解液被部署在双电子氧化还原液流电池中,该电池的电压高达 2.0 V,并且在 250 次循环中没有可检测到的交叉。