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Yan, Yong and O'Connor, Alice E. and Kanthasamy, Gopikkaa and Atkinson, George and Allan, David R. and 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

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.

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