Controlling the Crystallization of Porous Organic Cages: Molecular Analogs of Isoreticular Frameworks Using Shape-Specific Directing Solvents

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Hasell, Tom ORCID: 0000-0003-4736-0604, Culshaw, Jamie L, Chong, Sam ORCID: 0000-0002-3095-875X, Schmidtmann, Marc, Little, Marc, Jelfs, Kim E, Pyzer-Knapp, Edward O ORCID: 0000-0002-8232-8282, Shepherd, Hilary, Adams, Dave, Day, Graeme M et al (show 1 more authors) and Cooper, Andy (2014) Controlling the Crystallization of Porous Organic Cages: Molecular Analogs of Isoreticular Frameworks Using Shape-Specific Directing Solvents. Journal of the American Chemical Society, 136 (4). 1438 - 1448.

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Abstract

Small structural changes in organic moleculescan have a large influence onsolid-state crystal packing, and this often thwarts attempts to produce isostructuralseries of crystalline solids. For metal-organic frameworksand cova-lent organic frameworks, this has been addressed byusing strong,directional intermolecular bonding to create families of isoreticular solids. Here we show that an organic directing solvent, 1,4-dioxane, has a dominant effect on the lattice ener-gy for a series of organic cage molecules. Inclusion of dioxane directs the crystal packing for these cages awayfrom theirlowest-energy polymorphsto form isostructural, 3-dimensional diamondoid pore channels. This is a unique function of the size, chemical function, and geometry of 1,4-dioxane, and hence a non-covalent auxiliary interaction assumesthe role of directional coordination bonding or covalent bonding in extended crystalline frameworks. For a new cage, CC13, a dual, interpenetrating pore structure is formed which doubles the gas uptake and the surface area in the resulting dioxane-directed crystals.

Item Type:	Article
Uncontrolled Keywords:	Porous organic cages, covalent organic frameworks, metal-organic frameworks, crystalline; amorphous, microporous; polymorph
Depositing User:	Symplectic Admin
Date Deposited:	18 Feb 2015 11:07
Last Modified:	11 Jan 2022 00:10
DOI:	10.1021/ja409594s
Related URLs:	Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/2007109