In the past decade, the incorporation of tellurophene motifs into organic devices has been a promising strategy for the design of advanced materials. However, fundamental redox behavior of tellurophene-containing materials have never been comprehensively explored. Here, we report unique redox behavior of π-extended tellurophenes. The facile coordination of solvent molecules and/or anions becomes evident, in addition to the attachment of nucleophilic halides. This indicates that the tellurium center in oxidized 2,5-diphenyltellurophene is highly electron-deficient and easily yields coordinated structures. This coordination appears to trap the positive charge on the tellurium center rather than delocalizing it over the π-system. When no coordinating counter ion is present, however, oxidation appears to be delocalized over the entire π-system. Additionally, by using more delocalized structures, we show that coordination and charge-delocalization can co-exist. These results provide important insights to understand the properties of tellurophene-containing molecules and materials with extended π-systems.

在过去的十年中，将碲二酚基序并入有机设备中一直是设计先进材料的有前途的策略。但是，尚未全面探讨含碲二苯醚材料的基本氧化还原行为。在这里，我们报告π扩展碲二苯酚的独特氧化还原行为。除了亲核卤化物的附着之外，溶剂分子和/或阴离子的容易配位变得明显。这表明被氧化的2,5-二苯基二茂铁中的碲中心高度缺乏电子，容易产生配位结构。这种配位似乎是将正电荷捕获在碲中心，而不是使其在π系统上离域。但是，当不存在配位抗衡离子时，氧化作用似乎会在整个π系统上分散。此外，通过使用更多的离域结构，我们证明了协调和电荷离域可以共存。这些结果提供了重要的见解，以了解含碲烯的分子和具有扩展π系统的材料的特性。