Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
BCSJ Award Article
Solid-State Esterification via Ionic-to-Covalent Bond Transformation in Ionic Molecular Crystals Consisting of Disubstituted Anthracene Anion-Cation Combinations
Masato SuzukiTakahiro FujiiYoko NaitoKazuhisa YamotoShin-ichi MatsuokaKoji TakagiHaruki SugiyamaHidehiro Uekusa
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2018 Volume 91 Issue 3 Pages 343-348


Thermal solid-state reactions involving ionic-to-covalent bond transformation were achieved in the ionic molecular crystals of 1,8-bis[(pyridin-1-ium-1-yl)methyl]anthracene anthracene-1,8-dicarboxylate to produce the cyclic diester. The crystal structure given by X-ray diffraction analysis showed that the electrostatic interaction between the benzyl pyridinium cation and the carboxylate anion successfully works to locate these reaction sites close to each other and that there are channels for crystalline solvents and the liberated pyridine to escape. Thereby, the cyclic diester was selectively formed by the crystal-to-crystal reaction, which was proven by powder XRD profiles and optical microscopic and SEM images of the crystals before and after the reaction. This is the first thermal crystal-to-crystal condensation reaction. Another ionic molecular crystal of 1,8-bis[(pyridin-1-ium-1-yl)methyl]anthracene anthraquinone-1,8-dicarboxylate was also studied. Therein, the corresponding cyclic diester was also obtained, but the crystals were transformed to amorphous solid by the reaction.

A thermal crystal-to-crystal reaction was achieved for the first time by ionic-to-covalent bond transformation even though it is a kind of condensation. The electrostatic interaction between the cation and the anion plays a strong role to locate the reaction sites close to each other in the ionic molecular crystal and arranges the molecular packing to promote the crystal-to-crystal reaction. Fullsize Image
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