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

Author:
Yan, Yong, O’Connor, Alice E., Kanthasamy, Gopikkaa, Atkinson, George, Allan, David R., Blake, Alexander J., Schröder, Martin
Source:
Journal of the American Chemical Society 2018 v.140 no.11 pp. 3952-3958
ISSN:
1520-5126
Subject:
chemical structure, compressibility, coordination polymers, influenza, ligands, topology, zirconium
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(μ₃-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.
Agid:
6033048