Isolation and Characterization of Persistent Radical Cation and Dication of 2,7-Bis(dianisylamino)pyrene

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• 作者：Ryohei Kurata ; Kazuyoshi Tanaka ; Akihiro Ito
• 刊名：Journal of Organic Chemistry
• 出版年：2016
• 出版时间：January 4, 2016
• 年：2016
• 卷：81
• 期：1
• 页码：137-145
• 全文大小：592K
• ISSN：1520-6904

文摘

Orbital interaction between 2,7-pyrenylene and two nitrogen redox-active centers effectively reduces the energy difference between HOMO and HOMO–1, both of which were distributed over the two nitrogen centers. In fact, one- and two-electron oxidation of 2,7-bis(dianisylamino)pyrene 3 generated a persistent radical cation and a persistent dication, respectively, and we succeeded in the isolation and single crystal X-ray structural analyses of all three oxidation states. The radical cation was considered as a spin and charge delocalized mixed-valence compound with a semiquinoidal structure. The dication was in an open-shell singlet state with a small singlet–triplet energy gap. The molecular and electronic structures for all three oxidation states of 3 were studied in comparison with the data reported for each oxidation state of closely related bis(triarylamine)s, of which structures were determined by X-ray crystallography.