Design of crystalline spaces for molecular rotations in crystals

Zun Qi Liu, Kazuya Kubo, Shin Ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura

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    21 Citations (Scopus)


    4-Methylanilinium derivatives were used to introduce spaces for molecular rotation in crystals. The [Ni(dmit)2]- (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate) salts with supramolecular cations of dibenzo[18]crown-6 (DB[18]crown-6) and 4-methylanilinium derivatives, (4-methylanilinium+)(DB[18]crown-6)[Ni(dmit)2] - (1), (2-fluoro-4-methylanilinium+)(DB[18]crown-6) [Ni(dmit)2]- (2), and (3-fluoro-4-methylanilinium +)(DB[18]crown-6)[Ni(dmit)2]- (3) were synthesized. The potential energy curves for the molecular rotations of the cations in the crystals had double minimum shapes with maxima of 100, 210, and 230 kJ mol-1 for crystals 1, 2, and 3, respectively. Introduction of a methyl substituent at the p-position was effective in reducing the potential energy maxima. For crystals 2 and 3, large dielectric responses originating from the flip-flop motions of the cationic molecules were observed upon applying an AC voltage. The temperature-dependent magnetic susceptibilities of complexes 1, 2, and 3 followed the Curie-Weiss law, showing weak antiferromagnetic interactions.

    Original languageEnglish
    Pages (from-to)537-543
    Number of pages7
    JournalCrystal Growth and Design
    Issue number2
    Publication statusPublished - 2014 Feb 5

    ASJC Scopus subject areas

    • Chemistry(all)
    • Materials Science(all)
    • Condensed Matter Physics


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