Majewski Marcin A, Chmielewski Piotr J, Chien Alan, Hong Yongseok, Lis Tadeusz, Witwicki Maciej, Kim Dongho, Zimmerman Paul M, Stępień Marcin
Wydział Chemii , Uniwersytet Wrocławski , ul. F. Joliot-Curie 14 , 50-383 Wrocław , Poland . Email:
Department of Chemistry , University of Michigan , 930 N. University Ave , Ann Arbor , MI 48109 , USA . Email:
Chem Sci. 2019 Feb 7;10(11):3413-3420. doi: 10.1039/c9sc00170k. eCollection 2019 Mar 21.
A diindenophenanthrene biradicaloid, formally derived from Chichibabin's hydrocarbon, is obtained in a short, scalable synthesis. The present system is electron-rich and devoid of conjugated substituents, and still exhibits very good stability under ambient conditions. The introduction of the diindeno[1,2-:2',1'-] phenanthrene ring framework results in a singlet biradicaloid system with an easily accessible triplet state (Δ = -1.30 kcal mol) and a small electronic bandgap (1.39 V). The stability limits of the title hydrocarbon were explored systematically in the solid state, to reveal an unusual thermally initiated hydrogen-scrambling oligomerization process.
一种二茚并菲双自由基类化合物，形式上由奇奇巴宾烃衍生而来，可通过简短、可扩展的合成方法得到。本体系富含电子且无共轭取代基，在环境条件下仍表现出非常好的稳定性。二茚并[1,2-:2',1'-]菲环骨架的引入导致了一个单重态双自由基类体系，其具有易于获得的三重态（Δ = -1.30千卡/摩尔）和小的电子带隙（1.39伏）。系统地研究了标题烃在固态下的稳定性极限，以揭示一种不寻常的热引发氢重排齐聚过程。
