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

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23 Citations (Scopus)

Abstract

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
Volume81
Issue number7
DOIs
Publication statusPublished - 2016 Apr 15

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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    Hu, P., Lee, S., Park, K. H., Das, S., Herng, T. S., Gonçalves, T. P., Huang, K. W., Ding, J., Kim, D., & Wu, J. (2016). Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure. Journal of Organic Chemistry, 81(7), 2911-2919. https://doi.org/10.1021/acs.joc.6b00172