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Computationally-guided synthetic control over pore size in isostructural porous organic cages

Computationally-guided synthetic control over pore size in isostructural porous organic cages
Computationally-guided synthetic control over pore size in isostructural porous organic cages
The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal-organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of cage molecule, CC3, in a systematic way by introducing methyl groups into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure–energy landscape of a CC15-R binary co-crystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy–structure–function maps.
2374-7951
Slater, A.G.
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Reiss, P.S.
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Pulido, A.
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Little, M.A.
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Holden, D.L.
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Chen, L.
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Chong, S.Y.
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Alston, B.M.
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Clowes, R.
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Haranczyk, M.
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Briggs, M.E.
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Hasell, T.
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Day, G.M.
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Cooper, A.I.
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Slater, A.G.
09234a02-245a-4ab5-953c-3ffd7454cf63
Reiss, P.S.
59f0cb03-e20b-48d3-b0c2-efa8f7ac061b
Pulido, A.
cdc804ed-2c64-4f41-85f9-b8fadc2940b6
Little, M.A.
495763a7-c3f6-4ee0-b250-4b4e39c4350f
Holden, D.L.
fb45b68f-c1d7-44a7-9ec9-eee0fc0373e8
Chen, L.
90ca86d3-93ca-4771-9e58-0caed0bdb4c7
Chong, S.Y.
2e23eea0-c8eb-48bb-8e69-7f3a50d0e812
Alston, B.M.
9418e5d1-e452-4fd3-a372-82f27f3210e4
Clowes, R.
11e42a35-d9b1-44be-84af-10a5bac63b00
Haranczyk, M.
6d847c18-7de1-4d72-b77f-4fd81bf11dea
Briggs, M.E.
0127339e-85e0-459b-b76f-c91c4a5d61cf
Hasell, T.
6c8f5286-f4e2-456e-a3cd-dcfd3d164e52
Day, G.M.
e3be79ba-ad12-4461-b735-74d5c4355636
Cooper, A.I.
252b0212-4ed1-47ae-a8ea-6e745a95d2f4

Slater, A.G., Reiss, P.S., Pulido, A., Little, M.A., Holden, D.L., Chen, L., Chong, S.Y., Alston, B.M., Clowes, R., Haranczyk, M., Briggs, M.E., Hasell, T., Day, G.M. and Cooper, A.I. (2017) Computationally-guided synthetic control over pore size in isostructural porous organic cages. ACS Central Science. (doi:10.1021/acscentsci.7b00145).

Record type: Article

Abstract

The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal-organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of cage molecule, CC3, in a systematic way by introducing methyl groups into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure–energy landscape of a CC15-R binary co-crystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy–structure–function maps.

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Accepted/In Press date: 5 June 2017
e-pub ahead of print date: 20 June 2017
Organisations: Computational Systems Chemistry

Identifiers

Local EPrints ID: 411629
URI: https://eprints.soton.ac.uk/id/eprint/411629
ISSN: 2374-7951
PURE UUID: eaf6f5f2-c842-4400-8a2a-0b1fa8345f08
ORCID for A. Pulido: ORCID iD orcid.org/0000-0002-7596-7262
ORCID for G.M. Day: ORCID iD orcid.org/0000-0001-8396-2771

Catalogue record

Date deposited: 21 Jun 2017 16:31
Last modified: 14 Mar 2019 05:51

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Contributors

Author: A.G. Slater
Author: P.S. Reiss
Author: A. Pulido ORCID iD
Author: M.A. Little
Author: D.L. Holden
Author: L. Chen
Author: S.Y. Chong
Author: B.M. Alston
Author: R. Clowes
Author: M. Haranczyk
Author: M.E. Briggs
Author: T. Hasell
Author: G.M. Day ORCID iD
Author: A.I. Cooper

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