Radical polymers are promising redox-active materials for various potential energy storage, energy conversion, and magnetic field-dependent applications owing to the presence of the singularly occupied molecular orbitals that take part in redox exchange reactions and carry distinct magnetic moments. However, this redox exchange, which also promotes solid-state electronic conductivity, can be more pronounced if these radicals are spatially close to one another. Therefore, designing materials with nearer radical spacings is an open opportunity for significant molecular design advancement. To synthesize radical polymers with regiospecific control, we employed topochemical copolymerization of diacetylene comonomers in a coassembled gel consisting of a diacetylene functionalized gelator and a nongelling 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) diacetylene. As designed, the coassembled gel underwent topochemical copolymerization, yielding porous TEMPO-bearing polydiacetylene polymers. The radical-to-radical distance was <5.8 Å, and this led the radical polymer to exhibit an electrical conductivity of ∼2.5 × 10^–3 S m^–1. Because of the fibrous network structures, these radical polymers may be suitable for mixed conduction systems (e.g., energy storage devices) where both high electrical and ionic conductivity values are desired.

中文翻译：

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导电自由基聚合物的拓扑化学合成


由于存在参与氧化还原交换反应并携带不同磁矩的奇异占据分子轨道，自由基聚合物是用于各种势能存储、能量转换和磁场相关应用的有前景的氧化还原活性材料。然而，如果这些自由基在空间上彼此靠近，这种也促进固态电子传导性的氧化还原交换可能会更加明显。因此，设计具有更接近自由基间距的材料是显着分子设计进步的开放机会。为了合成具有区域特异性控制的自由基聚合物，我们在由丁二炔官能化胶凝剂和非胶凝2,2,6,6-四甲基哌啶氧基（TEMPO）二乙炔组成的共组装凝胶中采用了丁二炔共聚单体的拓扑化学共聚。按照设计，共组装凝胶经历了拓扑化学共聚，产生了多孔的带有 TEMPO 的聚二乙炔聚合物。自由基间距离为<5.8 Å，这使得自由基聚合物表现出～2.5 × 10 ^–3 S m ^–1 的电导率。由于纤维网络结构，这些自由基聚合物可能适用于需要高电导率和离子电导率值的混合传导系统（例如能量存储装置）。