Bis(aminoaryl) Carbon-Bridged Oligo(phenylenevinylene)s Expand the Limits of Electronic Couplings
Bis(aminoaryl) Carbon-Bridged Oligo(phenylenevinylene)s Expand the Limits of Electronic Couplings
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DOI：
10.1002/anie.201610921
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发表时间：
2017-03-06
影响因子：
16.6
通讯作者：
Casado, Juan
中科院分区：
文献类型：
--
作者：
Mayorga Burrezo, Paula;Lin, Nai-Ti;Casado, Juan
制备了碳桥联的双（氨基芳基）低聚（对亚苯基亚乙烯基），并分析了它们的光学、电化学和结构特性。它们的自由基阳离子是 III 类和 II 类混合价系，具体取决于分子大小，并且它们显示出纯有机分子自交换反应中最大的电子耦合。在它们的指示状态下，反铁磁耦合的尺寸从醌型闭壳到开壳双自由基逐渐调整。数据证明，自由基阳离子中的电子耦合和双峰中的单重态-三重态间隙显示出类似的小衰减因子，从而允许电荷/自旋转移在相当长的距离上。
Carbon-bridged bis(aminoaryl) oligo(para-phenylenevinylene)s have been prepared and their optical, electro-chemical, and structural properties analyzed. Their radical cations are class III and class II mixed-valence systems, depending on the molecular size, and they show electronic couplings which are among the largest for the self-exchange reaction of purely organic molecules. In their dication states, the antiferromagnetic coupling is progressively tuned with size from quinoidal closed-shell to open-shell biradicals. The data prove that the electronic coupling in the radical cations and the singlet-triplet gap in the dications show similar small attenuation factors, thus allowing charge/spin transfer over rather large distances.