An expandable hydrogen-bonded organic framework characterized by three-dimensional electron diffraction
An expandable hydrogen-bonded organic framework characterized by three-dimensional electron diffraction
A molecular crystal of a 2-D hydrogen-bonded organic framework (HOF) undergoes an unusual structural transformation after solvent removal from the crystal pores during activation. The conformationally flexible host molecule, ABTPA, adapts its molecular conformation during activation to initiate a framework expansion. The microcrystalline activated phase was characterized by three-dimensional electron diffraction (3D ED), which revealed that ABTPA uses out-of-plane anthracene units as adaptive structural anchors. These units change orientation to generate an expanded, lower density framework material in the activated structure. The porous HOF, ABTPA-2, has robust dynamic porosity (SABET = 1183 m2 g-1) and exhibits negative area thermal expansion. We use crystal structure prediction (CSP) to understand the underlying energetics behind the structural transformation and discuss the challenges facing CSP for such flexible molecules.
12743-12750
Cui, Peng
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Grape, Erik Svensson
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Spackman, Peter
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Wu, Yue
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Clowes, Rob
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Day, Graeme M.
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Inge, A. Ken
b0465771-f4d5-4488-b9da-32bd9cdd8bbb
Little, Marc A.
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Cooper, Andrew I
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22 July 2020
Cui, Peng
5d181dda-0fe7-4046-b6ab-459302250484
Grape, Erik Svensson
e26c7029-1bb2-4c8c-aaf8-b2bd6c21cc0b
Spackman, Peter
0b8d8f08-0b3b-45ce-8607-dafa10f28afe
Wu, Yue
c5742488-4034-4697-acea-1df46dc0441f
Clowes, Rob
11e42a35-d9b1-44be-84af-10a5bac63b00
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Inge, A. Ken
b0465771-f4d5-4488-b9da-32bd9cdd8bbb
Little, Marc A.
2499da90-f2de-4179-a41e-4931b3409584
Cooper, Andrew I
8cad6e52-32d3-487b-98e3-3f01cec43553
Cui, Peng, Grape, Erik Svensson, Spackman, Peter, Wu, Yue, Clowes, Rob, Day, Graeme M., Inge, A. Ken, Little, Marc A. and Cooper, Andrew I
(2020)
An expandable hydrogen-bonded organic framework characterized by three-dimensional electron diffraction.
Journal of the American Chemical Society, 142 (29), .
(doi:10.1021/jacs.0c04885).
Abstract
A molecular crystal of a 2-D hydrogen-bonded organic framework (HOF) undergoes an unusual structural transformation after solvent removal from the crystal pores during activation. The conformationally flexible host molecule, ABTPA, adapts its molecular conformation during activation to initiate a framework expansion. The microcrystalline activated phase was characterized by three-dimensional electron diffraction (3D ED), which revealed that ABTPA uses out-of-plane anthracene units as adaptive structural anchors. These units change orientation to generate an expanded, lower density framework material in the activated structure. The porous HOF, ABTPA-2, has robust dynamic porosity (SABET = 1183 m2 g-1) and exhibits negative area thermal expansion. We use crystal structure prediction (CSP) to understand the underlying energetics behind the structural transformation and discuss the challenges facing CSP for such flexible molecules.
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Accepted/In Press date: 27 June 2020
e-pub ahead of print date: 27 June 2020
Published date: 22 July 2020
Additional Information:
Funding Information:
For funding, the authors acknowledge the Engineering and Physical Sciences Research Council (EPSRC) (EP/N004884/1) and the Leverhulme Trust via the Leverhulme Research Centre for Functional Materials Design. P.C. thanks the China Scholarship Council for a PhD studentship. E.S.G. and A.K.I. acknowledge the Swedish Foundation for Strategic Research (SSF) and the Knut and Alice Wallenberg Foundation (KAW 2016.0072). The authors acknowledge Diamond Light Source for access to beamlines I19 (CY21726) and I11 (CY23666). We acknowledge the use of the IRIDIS High Performance Computing Facility and associated support services at the University of Southampton.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
Identifiers
Local EPrints ID: 442088
URI: http://eprints.soton.ac.uk/id/eprint/442088
ISSN: 0002-7863
PURE UUID: 03d7433a-5dac-44cd-a730-802c69c3f603
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Date deposited: 07 Jul 2020 16:48
Last modified: 17 Mar 2024 05:42
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Contributors
Author:
Peng Cui
Author:
Erik Svensson Grape
Author:
Peter Spackman
Author:
Yue Wu
Author:
Rob Clowes
Author:
A. Ken Inge
Author:
Marc A. Little
Author:
Andrew I Cooper
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