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 63 -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 languageEnglish
    Pages (from-to)3952-3958
    Number of pages7
    JournalJournal of the American Chemical Society
    Volume140
    Issue number11
    Early online date2 Feb 2018
    DOIs
    Publication statusPublished - 2 Feb 2018

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