Supramolecular engineering of intrinsic and extrinsic porosity in covalent organic cages

Bojdys, M. J., Briggs, M. E., Jones, J. T. A., Adams, D. J. , Chong, S. Y., Schmidtmann, M. and Cooper, A. I. (2011) Supramolecular engineering of intrinsic and extrinsic porosity in covalent organic cages. Journal of the American Chemical Society, 133(41), pp. 16566-16571. (doi: 10.1021/ja2056374) (PMID:21899280)

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Abstract

Control over pore size, shape, and connectivity in synthetic porous materials is important in applications such as separation, storage, and catalysis. Crystalline organic cage molecules can exhibit permanent porosity, but there are few synthetic methods to control the crystal packing and hence the pore connectivity. Typically, porosity is either ‘intrinsic’ (within the molecules) or ‘extrinsic’ (between the molecules)—but not both. We report a supramolecular approach to the assembly of porous organic cages which involves bulky directing groups that frustrate the crystal packing. This generates, in a synthetically designed fashion, additional ‘extrinsic’ porosity between the intrinsically porous cage units. One of the molecular crystals exhibits an apparent Brunauer–Emmett–Teller surface area of 854 m2 g–1, which is higher than that of unfunctionalized cages of the same dimensions. Moreover, connectivity between pores, and hence guest uptakes, can be modulated by the introduction of halogen bonding motifs in the cage modules. This suggests a broader approach to the supramolecular engineering of porosity in molecular organic crystals.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Schmidtmann, Mr Marc and Adams, Dave
Authors: Bojdys, M. J., Briggs, M. E., Jones, J. T. A., Adams, D. J., Chong, S. Y., Schmidtmann, M., and Cooper, A. I.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Published Online:07 September 2011

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