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Controlling the crystallization of porous organic cages: molecular analogs of isoreticular frameworks using shape-specific directing solvents

Controlling the crystallization of porous organic cages: molecular analogs of isoreticular frameworks using shape-specific directing solvents
Controlling the crystallization of porous organic cages: molecular analogs of isoreticular frameworks using shape-specific directing solvents
Small structural changes in organic molecules can have a large influence on solid-state crystal packing, and this often thwarts attempts to produce isostructural series of crystalline solids. For metal–organic frameworks and covalent organic frameworks, this has been addressed by using 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 energy for a series of organic cage molecules. Inclusion of dioxane directs the crystal packing for these cages away from their lowest-energy polymorphs to 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 noncovalent auxiliary interaction assumes the role of directional coordination bonding or covalent bonding in extended crystalline frameworks. For a new cage, CC13, a dual, interpenetrating pore structure is formed that doubles the gas uptake and the surface area in the resulting dioxane-directed crystals.
0002-7863
1438-1448
Hasell, Tom
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Culshaw, Jamie L.
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Chong, Samantha Y.
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Little, Marc A.
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Jelfs, Kim E.
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Pyzer-Knapp, Edward O.
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Shepherd, Hilary
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Adams, Dave J.
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Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Cooper, Andrew I.
95618a3b-7f3f-4731-a0d4-0a7b7ce07302
Hasell, Tom
6c8f5286-f4e2-456e-a3cd-dcfd3d164e52
Culshaw, Jamie L.
9ca17352-c2e7-4be9-b491-1119e9f0081c
Chong, Samantha Y.
2e23eea0-c8eb-48bb-8e69-7f3a50d0e812
Little, Marc A.
2499da90-f2de-4179-a41e-4931b3409584
Jelfs, Kim E.
342566a9-c513-43b2-9dee-9eb17ae446c0
Pyzer-Knapp, Edward O.
6a449b48-fce5-463a-8293-abb66b750ece
Shepherd, Hilary
e47e0f24-7b27-4a50-86e0-3f7aaa436785
Adams, Dave J.
d95e4f11-7580-43cb-802d-ad8ac0161c8a
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Cooper, Andrew I.
95618a3b-7f3f-4731-a0d4-0a7b7ce07302

Hasell, Tom, Culshaw, Jamie L., Chong, Samantha Y., Little, Marc A., Jelfs, Kim E., Pyzer-Knapp, Edward O., Shepherd, Hilary, Adams, Dave J., Day, Graeme M. and Cooper, Andrew I. (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. (doi:10.1021/ja409594s).

Record type: Article

Abstract

Small structural changes in organic molecules can have a large influence on solid-state crystal packing, and this often thwarts attempts to produce isostructural series of crystalline solids. For metal–organic frameworks and covalent organic frameworks, this has been addressed by using 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 energy for a series of organic cage molecules. Inclusion of dioxane directs the crystal packing for these cages away from their lowest-energy polymorphs to 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 noncovalent auxiliary interaction assumes the role of directional coordination bonding or covalent bonding in extended crystalline frameworks. For a new cage, CC13, a dual, interpenetrating pore structure is formed that doubles the gas uptake and the surface area in the resulting dioxane-directed crystals.

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e-pub ahead of print date: 10 January 2014
Published date: 29 January 2014
Additional Information: Funded by EPSRC: Chemical Synthesis of Transformative Extended Materials (EP/H000925/1) Materials Chemistry High End Computing Consortium (EP/L000202/1)
Organisations: Chemistry

Identifiers

Local EPrints ID: 362328
URI: http://eprints.soton.ac.uk/id/eprint/362328
ISSN: 0002-7863
PURE UUID: 6a71bde1-9eb0-421c-a06d-1934f5093e6e
ORCID for Graeme M. Day: ORCID iD orcid.org/0000-0001-8396-2771

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Date deposited: 20 Feb 2014 13:25
Last modified: 03 Dec 2019 01:38

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Contributors

Author: Tom Hasell
Author: Jamie L. Culshaw
Author: Samantha Y. Chong
Author: Marc A. Little
Author: Kim E. Jelfs
Author: Edward O. Pyzer-Knapp
Author: Hilary Shepherd
Author: Dave J. Adams
Author: Graeme M. Day ORCID iD
Author: Andrew I. Cooper

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