Macromolecular radicals are receiving growing interest as functional materials in energy storage devices and in electronics. With the need for enhanced conductivity, researchers have turned to macromolecular radicals bearing conjugated backbones, but results thus far have yielded conjugated radical polymers that are inferior in comparison to their non-conjugated partners. The emerging explanation is that the radical unit and the conjugated backbone (both being redox active) transfer electrons between each other, essentially “quenching” conductivity or capacity. Here, the internal charge transfer process is quantified using a polythiophene loaded with 0, 25, or 100% nitroxide radicals (2,2,6,6-tetramethyl-1-piperidinyloxy [TEMPO]). Importantly, deconvolution of the cyclic voltammograms shows mixed faradaic and non-faradaic contributions that contribute to the internal charge transfer process. Further, mixed ion-electron transfer is determined for the 100% TEMPO-loaded conjugated radical polymer, from which it is estimated that one triflate anion and one propylene carbone molecule are exchanged for every electron. Although these findings indicate the reason behind their poor conductivity and capacity, they point to how these materials might be used as voltage regulators in the future.

中文翻译：

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定量共轭自由基聚合物中的内部电荷转移和离子电子混合转移

高分子自由基在能量存储设备和电子产品中作为功能材料正受到越来越多的关注。由于需要提高电导率，研究人员已转向带有共轭主链的大分子自由基，但到目前为止的结果是，共轭自由基聚合物的性能比非共轭伴侣低。新兴的解释是，自由基单元和共轭主链（均为氧化还原活性）彼此之间转移电子，实质上是“猝灭”了电导率或电容。在此，内部电荷转移过程是使用装有0、25或100％的氮氧自由基（2,2,6,6-四甲基-1-哌啶基氧基[TEMPO]）的聚噻吩进行定量的。重要的，循环伏安图的反卷积显示法拉第和非法拉第的混合贡献有助于内部电荷转移过程。此外，对于100％TEMPO负载的共轭自由基聚合物，确定了混合的离子-电子转移，据估计，每个电子交换一个三氟甲磺酸根阴离子和一个丙烯碳原子分子。尽管这些发现表明了其导电性和容量差的原因，但它们指出了这些材料将来如何用作稳压器。