Unusual and Tunable Negative Linear Compressibility in the Metal–Organic Framework MFM-133(M) (M = Zr, Hf)

Yong Yan; Alice E. O'Connor; Gopikkaa  Kanthasamy; George  Atkinson; David R. Allan; Alexander J. Blake; Martin Schroder

doi:10.1021/jacs.7b11747

Unusual and Tunable Negative Linear Compressibility in the Metal–Organic Framework MFM-133(M) (M = Zr, Hf)

Yong Yan, Alice E. O'Connor, Gopikkaa Kanthasamy, George Atkinson, David R. Allan, Alexander J. Blake, Martin Schroder

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Abstract

High-pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB ^4- [H ₄ TCHB = 3,3′,5,5′-tetrakis(4-carboxyphenyl)-2,2′,4,4′,6,6′-hexamethyl-1,1′-biphenyl] and {M ₆ (μ ₃ -OH) ₈ (OH) ₈ (COO) ₈ } clusters confirm negative linear compressibility (NLC) behavior along the c axis. This occurs via a three-dimensional wine-rack NLC mechanism leading to distortion of the octahedral cage toward 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.

Original language	English
Pages (from-to)	3952-3958
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	140
Issue number	11
Early online date	2 Feb 2018
DOIs	https://doi.org/10.1021/jacs.7b11747
Publication status	Published - 2 Feb 2018

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CCDC 1581937: Experimental Crystal Structure Determination
Yan, Y. (Contributor), O'Connor, A. E. (Contributor), Kanthasamy, G. (Contributor), Atkinson, G. (Contributor), Allan, D. R. (Contributor), Blake, A. J. (Contributor) & Schroder, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2018
DOI: 10.5517/ccdc.csd.cc1q3476, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1q3476&sid=DataCite
Dataset
CCDC 1582079: Experimental Crystal Structure Determination
Yan, Y. (Contributor), O'Connor, A. E. (Contributor), Kanthasamy, G. (Contributor), Atkinson, G. (Contributor), Allan, D. R. (Contributor), Blake, A. J. (Contributor) & Schroder, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2018
DOI: 10.5517/ccdc.csd.cc1q38tx, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1q38tx&sid=DataCite
Dataset
CCDC 1582081: Experimental Crystal Structure Determination
Yan, Y. (Contributor), O'Connor, A. E. (Contributor), Kanthasamy, G. (Contributor), Atkinson, G. (Contributor), Allan, D. R. (Contributor), Blake, A. J. (Contributor) & Schroder, M. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2018
DOI: 10.5517/ccdc.csd.cc1q38wz, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1q38wz&sid=DataCite
Dataset

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@article{b42b9d7d9d374827a02e86390c6d16e2,

title = "Unusual and Tunable Negative Linear Compressibility in the Metal–Organic Framework MFM-133(M) (M = Zr, Hf)",

abstract = "High-pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB 4- [H 4 TCHB = 3,3′,5,5′-tetrakis(4-carboxyphenyl)-2,2′,4,4′,6,6′-hexamethyl-1,1′-biphenyl] and {M 6 (μ 3 -OH) 8 (OH) 8 (COO) 8 } clusters confirm negative linear compressibility (NLC) behavior along the c axis. This occurs via a three-dimensional wine-rack NLC mechanism leading to distortion of the octahedral cage toward 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. ",

author = "Yong Yan and O'Connor, {Alice E.} and Gopikkaa Kanthasamy and George Atkinson and Allan, {David R.} and Blake, {Alexander J.} and Martin Schroder",

note = "Funding Information: We thank the EPSRC (EP/I011870), ERC (Advanced Grant AdG 226593), and the Universities of Manchester and Nottingham for funding. We are grateful to Diamond Light Source for access to Beamline I19. Publisher Copyright: {\textcopyright} 2018 American Chemical Society. Copyright: Copyright 2018 Elsevier B.V., All rights reserved.",

year = "2018",

month = feb,

day = "2",

doi = "10.1021/jacs.7b11747",

language = "English",

volume = "140",

pages = "3952--3958",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "11",

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T1 - Unusual and Tunable Negative Linear Compressibility in the Metal–Organic Framework MFM-133(M) (M = Zr, Hf)

AU - Yan, Yong

AU - O'Connor, Alice E.

AU - Kanthasamy, Gopikkaa

AU - Atkinson, George

AU - Allan, David R.

AU - Blake, Alexander J.

AU - Schroder, Martin

N1 - Funding Information: We thank the EPSRC (EP/I011870), ERC (Advanced Grant AdG 226593), and the Universities of Manchester and Nottingham for funding. We are grateful to Diamond Light Source for access to Beamline I19. Publisher Copyright: © 2018 American Chemical Society. Copyright: Copyright 2018 Elsevier B.V., All rights reserved.

PY - 2018/2/2

Y1 - 2018/2/2

N2 - High-pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB 4- [H 4 TCHB = 3,3′,5,5′-tetrakis(4-carboxyphenyl)-2,2′,4,4′,6,6′-hexamethyl-1,1′-biphenyl] and {M 6 (μ 3 -OH) 8 (OH) 8 (COO) 8 } clusters confirm negative linear compressibility (NLC) behavior along the c axis. This occurs via a three-dimensional wine-rack NLC mechanism leading to distortion of the octahedral cage toward 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.

AB - High-pressure single-crystal X-ray structural analyses of isostructural MFM-133(M) (M = Zr, Hf) of flu topology and incorporating the tetracarboxylate ligand TCHB 4- [H 4 TCHB = 3,3′,5,5′-tetrakis(4-carboxyphenyl)-2,2′,4,4′,6,6′-hexamethyl-1,1′-biphenyl] and {M 6 (μ 3 -OH) 8 (OH) 8 (COO) 8 } clusters confirm negative linear compressibility (NLC) behavior along the c axis. This occurs via a three-dimensional wine-rack NLC mechanism leading to distortion of the octahedral cage toward 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.

U2 - 10.1021/jacs.7b11747

DO - 10.1021/jacs.7b11747

M3 - Article

SN - 0002-7863

VL - 140

SP - 3952

EP - 3958

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 11

ER -

Unusual and Tunable Negative Linear Compressibility in the Metal–Organic Framework MFM-133(M) (M = Zr, Hf)

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CCDC 1581937: Experimental Crystal Structure Determination

CCDC 1582079: Experimental Crystal Structure Determination

CCDC 1582081: Experimental Crystal Structure Determination

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