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Exploiting Powder X‑ray Diffraction to Establish the Solvent-Assisted Solid-State Supramolecular Assembly of Pillar[5]quinone

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journal contribution
posted on 01.04.2015 by Kilingaru I. Shivakumar, Yuncheng Yan, Colan E. Hughes, David C. Apperley, Kenneth D. M. Harris, Gangadhar J. Sanjayan
We report the solvent-mediated supramolecular assembly of pillar[5]­quinone (P[5]­Q), a symmetric cyclamer containing five benzoquinone moieties bridged by five alternating methylene units. The supramolecular assembly of P[5]­Q is shown to be facilitated by 1,1,2,2-tetrachloroethane (TCE) as solvent, producing a microcrystalline solvate material P[5]­Q·2TCE with a fluffy texture. Optical and electron microscopy reveal that this material has a rod-shaped morphology, extending to several micrometers in length. Due to the microcrystalline nature of the material, structure determination was carried out directly from powder X-ray diffraction data, augmented by high-resolution solid-state 13C NMR. The two crystallographically distinct TCE molecules occupy different types of void in the structure and have different dynamic properties. Crystallization of P[5]­Q was attempted from a large number of different solvents, but only TCE was found to facilitate the formation of a crystalline phase. Indeed, features of the crystal structure suggest that the TCE component plays an important role in promoting the columnar assembly of P[5]­Q molecules.