Mayorga-Burrezo Paula, Bejarano Francesc, Calbo Joaquín, Zhao Xiaotao, De Sousa J Alejandro, Lloveras Vega, Bryce Martin R, Ortí Enrique, Veciana Jaume, Rovira Concepció, Crivillers Núria
Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus UAB, 08193 Bellaterra, Spain.
Instituto de Ciencia Molecular, Universidad de Valencia, Catedrático José Beltrán, 2, 46980 Paterna, Spain.
J Phys Chem Lett. 2021 Jul 8;12(26):6159-6164. doi: 10.1021/acs.jpclett.1c01565. Epub 2021 Jun 29.
Two redox and magnetically active perchlorotriphenylmethyl (PTM) radical units have been connected as end-capping groups to a bis(phenylene)diyne chain through vinylene linkers. Negative and positive charged species have been generated, and the influence of the bridge on their stabilization is discussed. Partial reduction of the electron-withdrawing PTM radicals results in a class-II mixed-valence system with the negative charge located on the terminal PTM units, proving the efficiency of the conjugated chain for the electron transport between the two terminal sites. Counterintuitively, the oxidation process does not occur along the electron-rich bridge but on the vinylene units. The PTM radicals play a key role in the stabilization of the cationic species, promoting the generation of quinoidal ring segments.
两个具有氧化还原活性和磁性的过氯三苯甲基（PTM）自由基单元通过亚乙烯基连接体作为封端基团连接到双（亚苯基）二炔链上。已生成带负电荷和正电荷的物种，并讨论了桥对它们稳定性的影响。吸电子的PTM自由基的部分还原导致形成II类混合价体系，负电荷位于末端PTM单元上，证明了共轭链在两个末端位点之间进行电子传输的效率。与直觉相反，氧化过程不是沿着富电子的桥发生，而是在亚乙烯基单元上发生。PTM自由基在阳离子物种的稳定中起关键作用，促进醌型环段的生成。
