Inserting nitrogen: An effective concept to create nonplanar and stimuli-responsive perylene bisimide analogues

Sakiho Hayakawa, Ayumi Kawasaki, Yongseok Hong, Daisuke Uraguchi, Takashi Ooi, Dongho Kim, Tomoyuki Akutagawa, Norihito Fukui, Hiroshi Shinokubo

    Research output: Contribution to journalArticlepeer-review

    18 Citations (Scopus)


    Establishing design principles to create nonplanar π-conjugated molecules is crucial for the development of novel functional materials. Herein, we describe the synthesis and properties of dinaphtho-[1,8-bc:1′,8′-ef ]azepine bisimides (DNABIs). Their molecular design is conceptually based on the insertion of a nitrogen atom into a perylene bisimide core. We have synthesized several DNABI derivatives with a hydrogen atom, a primary alkyl group, or an aryl group on the central nitrogen atom. These DNABIs exhibit nonplanar conformations, flexible structural changes, and ambipolar redox activity. The steric effect around the central nitrogen atom substantially affects the overall structures and results in two different conformations: a nonsymmetric bent conformation and a symmetric twisted conformation, accompanied by a drastic change in electronic properties. Notably, the nonsymmetric DNABI undergoes unique structural changes in response to the application of an external electric field, which is due to molecular motions that are accompanied by an orientational fluctuation of the dipole moment. Furthermore, the addition of a chiral Brønsted base to N-unsubstituted DNABI affords control over the helical chirality via hydrogen-bonding interactions.

    Original languageEnglish
    Pages (from-to)19807-19816
    Number of pages10
    JournalJournal of the American Chemical Society
    Issue number50
    Publication statusPublished - 2019 Dec 18

    ASJC Scopus subject areas

    • Catalysis
    • Chemistry(all)
    • Biochemistry
    • Colloid and Surface Chemistry


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