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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.; Schr�der, Martin

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


Authors

Yong Yan

Alice E. O'Connor

Gopikkaa Kanthasamy

George Atkinson

David R. Allan

Alexander J. Blake

Martin Schr�der



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 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.

Citation

Yan, Y., O'Connor, A. E., Kanthasamy, G., Atkinson, G., Allan, D. R., Blake, A. J., & Schröder, M. (in press). Unusual and tunable negative linear compressibility in the metal–organic framework MFM-133(M)(M = Zr, Hf). Journal of the American Chemical Society, https://doi.org/10.1021/jacs.7b11747

Journal Article Type Article
Acceptance Date Feb 2, 2018
Online Publication Date Feb 2, 2018
Deposit Date Feb 16, 2018
Publicly Available Date Feb 3, 2019
Journal Journal of the American Chemical Society
Print ISSN 0002-7863
Electronic ISSN 1520-5126
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
DOI https://doi.org/10.1021/jacs.7b11747
Public URL https://nottingham-repository.worktribe.com/output/908715
Publisher URL https://pubs.acs.org/doi/abs/10.1021/jacs.7b11747

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