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Hydrolytic stability in hemilabile metal–organic frameworks

Hydrolytic stability in hemilabile metal–organic frameworks
Hydrolytic stability in hemilabile metal–organic frameworks

Highly porous metal–organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of ‘sacrificial’ bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF’s copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.

1755-4330
1096-1102
McHugh, Lauren N.
cf4f6505-763b-478a-9170-6057e648f454
McPherson, Matthew J.
d3c78165-4cd3-4607-bdb4-465ce844bc96
McCormick, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Morris, Samuel A.
e1cae713-3787-412d-b7d0-02ad52eebb04
Wheatley, Paul S.
f8a43a65-3474-42c7-bf40-2e17db0c2415
Teat, Simon J.
fd6e6d90-b0c2-4463-91d2-5c72e212d414
McKay, David
ba1941a3-1784-4221-9cd6-cb9492e63981
Dawson, Daniel M.
b73d9ebe-ecf6-49ad-a205-a57bb9ed1e8c
Sansome, Charlotte E.F.
91028b1c-53c0-4a69-a24d-da37c61499b3
Ashbrook, Sharon E.
7f280ee4-6793-4956-aeb7-e933c8fafb1d
Stone, Corinne A.
82398e84-1fd2-4e8c-9950-140bdb618e37
Smith, Martin W.
f9f0b607-53c8-4f4c-9292-df31c36c7cf6
Morris, Russell E.
0c724305-d30c-4be8-8b1f-bec10ca5f91c
McHugh, Lauren N.
cf4f6505-763b-478a-9170-6057e648f454
McPherson, Matthew J.
d3c78165-4cd3-4607-bdb4-465ce844bc96
McCormick, Laura J.
f1c2f8cd-adcc-4bbf-9289-0b33a006d2bb
Morris, Samuel A.
e1cae713-3787-412d-b7d0-02ad52eebb04
Wheatley, Paul S.
f8a43a65-3474-42c7-bf40-2e17db0c2415
Teat, Simon J.
fd6e6d90-b0c2-4463-91d2-5c72e212d414
McKay, David
ba1941a3-1784-4221-9cd6-cb9492e63981
Dawson, Daniel M.
b73d9ebe-ecf6-49ad-a205-a57bb9ed1e8c
Sansome, Charlotte E.F.
91028b1c-53c0-4a69-a24d-da37c61499b3
Ashbrook, Sharon E.
7f280ee4-6793-4956-aeb7-e933c8fafb1d
Stone, Corinne A.
82398e84-1fd2-4e8c-9950-140bdb618e37
Smith, Martin W.
f9f0b607-53c8-4f4c-9292-df31c36c7cf6
Morris, Russell E.
0c724305-d30c-4be8-8b1f-bec10ca5f91c

McHugh, Lauren N., McPherson, Matthew J., McCormick, Laura J., Morris, Samuel A., Wheatley, Paul S., Teat, Simon J., McKay, David, Dawson, Daniel M., Sansome, Charlotte E.F., Ashbrook, Sharon E., Stone, Corinne A., Smith, Martin W. and Morris, Russell E. (2018) Hydrolytic stability in hemilabile metal–organic frameworks. Nature Chemistry, 10 (11), 1096-1102. (doi:10.1038/s41557-018-0104-x).

Record type: Article

Abstract

Highly porous metal–organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of ‘sacrificial’ bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF’s copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.

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More information

Accepted/In Press date: 11 June 2018
e-pub ahead of print date: 13 August 2018
Published date: 1 November 2018

Identifiers

Local EPrints ID: 438861
URI: http://eprints.soton.ac.uk/id/eprint/438861
ISSN: 1755-4330
PURE UUID: 2a248524-5397-4b11-a841-d42bc461d440
ORCID for Laura J. McCormick: ORCID iD orcid.org/0000-0002-6634-4717

Catalogue record

Date deposited: 25 Mar 2020 17:32
Last modified: 26 Nov 2021 03:21

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Contributors

Author: Lauren N. McHugh
Author: Matthew J. McPherson
Author: Samuel A. Morris
Author: Paul S. Wheatley
Author: Simon J. Teat
Author: David McKay
Author: Daniel M. Dawson
Author: Charlotte E.F. Sansome
Author: Sharon E. Ashbrook
Author: Corinne A. Stone
Author: Martin W. Smith
Author: Russell E. Morris

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