Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf)

High pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB4– [H4TCHB = 3,3',5,5'-tetrakis(4-carboxyphenyl)-2,2',4,4',6,6'-hexamethyl-1,1'-biphenyl] and {M6(μ-OH)8(OH)...

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Main Authors: Yan, Yong, O'Connor, Alice E., Kanthasamy, Gopikkaa, Atkinson, George, Allan, David R., Blake, Alexander J., Schröder, Martin
Format: Article
Published: American Chemical Society 2018
Online Access:https://eprints.nottingham.ac.uk/49819/
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author Yan, Yong
O'Connor, Alice E.
Kanthasamy, Gopikkaa
Atkinson, George
Allan, David R.
Blake, Alexander J.
Schröder, Martin
author_facet Yan, Yong
O'Connor, Alice E.
Kanthasamy, Gopikkaa
Atkinson, George
Allan, David R.
Blake, Alexander J.
Schröder, Martin
author_sort Yan, Yong
building Nottingham Research Data Repository
collection Online Access
description High pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB4– [H4TCHB = 3,3',5,5'-tetrakis(4-carboxyphenyl)-2,2',4,4',6,6'-hexamethyl-1,1'-biphenyl] and {M6(μ-OH)8(OH)8(COO)8} clusters, confirm negative linear compressibility (NLC) behavior along the c axis. This occurs via a three-dimensional winerack NLC mechanism leading to distortion of the octahedral cage towards a more elongated polyhedron under static compression. Despite the isomorphous nature of these two structures, MFM-133(Hf) shows a higher degree of NLC than the Zr(IV) analogue. Thus, for the first time, we demonstrate here that the NLC property can be effectively tuned in a framework material by simply varying the inorganic component of the frameworks without changing the network topology and structure.
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spelling nottingham-498192020-05-04T19:29:48Z https://eprints.nottingham.ac.uk/49819/ Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf) Yan, Yong O'Connor, Alice E. Kanthasamy, Gopikkaa Atkinson, George Allan, David R. Blake, Alexander J. Schröder, Martin High pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB4– [H4TCHB = 3,3',5,5'-tetrakis(4-carboxyphenyl)-2,2',4,4',6,6'-hexamethyl-1,1'-biphenyl] and {M6(μ-OH)8(OH)8(COO)8} clusters, confirm negative linear compressibility (NLC) behavior along the c axis. This occurs via a three-dimensional winerack NLC mechanism leading to distortion of the octahedral cage towards a more elongated polyhedron under static compression. Despite the isomorphous nature of these two structures, MFM-133(Hf) shows a higher degree of NLC than the Zr(IV) analogue. Thus, for the first time, we demonstrate here that the NLC property can be effectively tuned in a framework material by simply varying the inorganic component of the frameworks without changing the network topology and structure. American Chemical Society 2018-02-02 Article PeerReviewed Yan, Yong, O'Connor, Alice E., Kanthasamy, Gopikkaa, Atkinson, George, Allan, David R., Blake, Alexander J. and Schröder, Martin (2018) Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf). Journal of the American Chemical Society . ISSN 1520-5126 https://pubs.acs.org/doi/abs/10.1021/jacs.7b11747 doi:10.1021/jacs.7b11747 doi:10.1021/jacs.7b11747
spellingShingle Yan, Yong
O'Connor, Alice E.
Kanthasamy, Gopikkaa
Atkinson, George
Allan, David R.
Blake, Alexander J.
Schröder, Martin
Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf)
title Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf)
title_full Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf)
title_fullStr Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf)
title_full_unstemmed Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf)
title_short Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf)
title_sort unusual and tunable negative linear compressibility in the metal–organic framework mfm-133(m)(m = zr, hf)
url https://eprints.nottingham.ac.uk/49819/
https://eprints.nottingham.ac.uk/49819/
https://eprints.nottingham.ac.uk/49819/