Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

Pan Hu, Sangsu Lee, Kyu Hyung Park, Soumyajit Das, Tun Seng Herng, Théo P. Gonçalves, Kuo Wei Huang, Jun Ding, Dongho Kim, Jishan Wu

Research output: Contribution to journalArticlepeer-review

40 Citations (Scopus)


The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl-or pentafluorophenyl-substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability in an ambient environment, while OZI-M has high reactivity and can be easily oxidized to a dioxo product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F, and 15.

Original languageEnglish
Pages (from-to)2911-2919
Number of pages9
JournalJournal of Organic Chemistry
Issue number7
Publication statusPublished - 2016 Apr 15

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Organic Chemistry


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