Physical Properties of Metal-Organic Frameworks
Anthony K. Cheetham
Department of Materials Science and Metallurgy
University of Cambridge
Cambridge CB2 3QZ
Our current research on metal-organic frameworks (MOFs) focuses primarily on their
physical properties, including their mechanical, optical, magnetic, ferroelectric and electronic
behaviour. In the area of mechanical properties we have worked extensively on the
amorphization of MOFs [1], as well as on the impact of hydrogen bonding on the Young’s
modulus and hardness of perovskite-related MOFs [2]. I shall discuss several cases of phase
transitions that depend heavily on framework flexibility. These include the transition from a
porous to a dense framework at 160K in the Zeolitic Imidazolate Framework, ZIF-4, which is
accompanied by a decrease in volume of ~23% [3]. A second example involves a reversible,
pressure-induced phase transition in a dense rare-earth formate, which shows the breaking
and making of bonds during a transition that is accompanied by a 10% change in volume [4].
We shall also discuss the semiconducting hybrid perovskite, CH3NH3PbI3, which shows a
transition due to hydrogen bond ordering on cooling below 160 K [5]. Finally we shall
explore chemical transformations that depend on flexibility, such as the topochemical
dehalogenation of a copper trithiocyanurate framework that is accompanied by a change from
an insulating crystalline phase to an amorphous semiconductor [6], an insulator to proton
conductor transition that is driven by hydration [7], and glass formation by quenching liquid
ZIFs [8].
1. T. D. Bennett and A. K. Cheetham, Accounts of Chemical Research 47, 1555 (2014)
2. W. Li, E. G. Bithell, P. T. Barton, Z. Lin, A. Thirumurugan, S. Henke, H. H.-M. Yeung, M. T. Wharmby, C.
J. Howard and A. K. Cheetham, J. Amer. Chem. Soc. 136, 7801 (2014)
3. M. T. Wharmby, S. Henke, T. D. Bennett, Y. Yue, C. Mellot-Draznieks, and A. K. Cheetham, Angew. Chem.
Intl. Ed. 54, 6447 (2015)
4. E. C. Spencer, M. S. R. N. Kiran, Wei Li, U. Ramamurty, N. L. Ross and A. K. Cheetham, Angew. Chem.
Intl. Ed. 53, 5583 (2014)
5. J.-H. Lee, N. C. Bristowe, P. D. Bristowe, and A. K. Cheetham Chem. Comm. 51, 6434 (2015)
6. S. Tominaka, T. Suga, T. D. Bennett and A. K. Cheetham, Chem. Sci. 6, 1465 (2015)
7. S. Tominaka, F. X. Coudert, T. D. Dao, T. Nagao and A. K. Cheetham, J. Amer. Chem. Soc. 137, 6428
(2015).
8. T. D. Bennett, J. C. Tan, Y. Z. Yue, C. Ducati, N. Terrill, H.H.M. Yeung, Z. Zhou, S. Henke, A. K.
Cheetham and G. N. Greaves, Nature Comm. 6, 8079 (2015)
Professor Tony Cheetham
Department of Materials Science and
Metallurgy, University of Cambridge,
Cambridge CB3 0FS
akc30@cam.ac.uk
Tony Cheetham obtained his D.Phil. at Oxford in 1971 and did postdoctoral work in the Materials Physics Division at Harwell. He joined
the chemistry faculty at Oxford in 1974, and then moved to the
University of California at Santa Barbara in 1991 to become Professor
in the Materials Department. In 1992 he took up the Directorship of the
new Materials Research Laboratory, which he led for 12 years. He was
the Director of the new-created International Center for Materials
Research at UCSB, 2004-7, before moving to Cambridge to become
the Goldsmiths’ Professor of Materials Science. Cheetham is a Fellow
of the Royal Society, the German Academy of Sciences, the American
Academy of Arts and Sciences, and several other academies. He has
received numerous international awards for his work in the field of
inorganic and materials chemistry; these include a Chaire Blaise
Pascal, Paris, (1997-9), the Somiya Award of the IUMRS (2004), the
Leverhulme Medal of the Royal Society (2008), the Platinum Medal of
the IOM3 (2011), and a Chemical Pioneer Award from the American
Institute of Chemists (2014). Cheetham holds several honorary
doctorates and is currently the Treasurer and Vice-President of the
Royal Society