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

DOI: 10.1021/jacs.7b11747 DOI Help

Authors: Yong Yan (University of Manchester) , Alice E. O'connor (University of Nottingham) , Gopikkaa Kanthasamy (University of Southampton) , George Atkinson (University of Nottingham) , David R. Allan (Diamond Light Source) , Alexander J. Blake (University of Nottingham) , Martin Schröder (University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: February 2018
Diamond Proposal Number(s): 11361

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 wine-rack 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 an effective strategy for tuning NLC materials simply by varying the inorganic component of the frameworks.

Subject Areas: Chemistry, Materials

Diamond Offline Facilities: Pressure ruby luminescence spectrometer
Instruments: I19-Small Molecule Single Crystal Diffraction

Other Facilities: No