Synthesis of methoxy-substituted picenes: Substitution position effect on their electronic and single-crystal structures

Hiroki Mori, Xi Chao Chen, Ning Hui Chang, Shino Hamao, Yoshihiro Kubozono, Kiyohiko Nakajima, Yasushi Nishihara

    Research output: Contribution to journalArticlepeer-review

    27 Citations (Scopus)

    Abstract

    A series of picenes having methoxy groups was synthesized through Pd-catalyzed Suzuki-Miyaura couplings or Wittig reaction/intramolecular cyclization sequences, and their physicochemical properties and single-crystal structures were evaluated. The substitution position effects between the outer 1,12-, 2,11-, and 4,9-position and the inner 3,10-position are quite different; the former showed the same electronic structure as that of picene, but the latter results in a HOMO geometry different from those of picene and other methoxy picenes. In addition, crystal structures of four types of methoxy-substituted picenes 4a-c,e strongly depend on their substitution position and number of methoxy groups, which dramatically changes the structures from the fully anisotropic 1D π-stacked structure to a unique 3D herringbone structure due to steric hindrance of methoxy groups. The calculations of transfer integrals based on their single-crystal structures reveal that the methoxy picenes have intermolecular overlaps less effective than that of the parent nonsubstituted picene. These results are attributed not only to the packing structure but also to electronic structures such as the HOMO distribution. The preliminary OFET of the representative 4c,e showed hole mobilities significantly lower than that of picene due to their less effective intermolecular overlaps, as predicted by the calculated transfer integrals.

    Original languageEnglish
    Pages (from-to)4973-4983
    Number of pages11
    JournalJournal of Organic Chemistry
    Volume79
    Issue number11
    DOIs
    Publication statusPublished - Jun 6 2014

    ASJC Scopus subject areas

    • Organic Chemistry

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