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Supramolecular engineering of intrinsic and extrinsic porosity in covalent organic cages

DOI: 10.1021/ja2056374 DOI Help

Authors: Michael Bojdys (University of Liverpool) , Michael E. Briggs (University of Liverpool) , James Jones (University of Liverpool) , Dave Adams (University of Liverpool) , Sam Chong (University of Liverpool) , Marc Schmidtmann (University of Liverpool) , Andrew I. Cooper (University of Liverpool)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society , VOL 133 (41)

State: Published (Approved)
Published: September 2011

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 in-volves 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 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.

Subject Areas: Chemistry


Instruments: I11-High Resolution Powder Diffraction