journal article·2016-01-12

Role of Amine–Cavity Interactions in Determining the Structure and Mechanical Properties of the Ferroelectric Hybrid Perovskite [NH3NH2]Zn(HCOO)3

Gregor Kieslich, Alexander C. Forse, Shijing Sun, Keith T. Butler, Shohei Kumagai, Yue Wu, Mark R. Warren, Aron Walsh, Clare P. Grey, Anthony K. Cheetham

Chemistry of Materials· Volume 28· Issue 1
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Abstract

Dense formate frameworks with a perovskite-like architecture exhibit multiferroic behavior and tunable mechanical properties. In such materials, interactions between the protonated amine and the metal–formate cavity have a large impact on the mechanical properties. We use complementary single-crystal X-ray diffraction and 1 H solid state nuclear magnetic resonance spectroscopy to investigate amine–cavity interactions in [NH 3 NH 2 ]Zn(HCOO) 3 . The results suggest that these interactions can be described as salt bridges similar to those in proteins and artificially synthesized helical polymers, where ionic interactions and hydrogen bonds are present at the same time. Nanoindentation and high-pressure single-crystal X-ray diffraction were used to study the mechanical properties of [NH 3 NH 2 ]Zn(HCOO) 3, yielding elastic moduli of E 001 = 26.5 GPa and E 110 = 24.6 GPa and a bulk modulus of K = 19 GPa. The mechanical properties suggest that, despite the relatively low packing density of [NH 3 NH 2 ]Zn(HCOO) 3, the amine–cavity interactions strengthen the framework significantly in comparison with related materials.
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Research context

OpenAlex topics: Perovskite Materials and Applications · Solid-state spectroscopy and crystallography · Inorganic Fluorides and Related Compounds

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, U.K.

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.

Centre for Sustainable Chemical Technologies and Department of Chemistry, University of Bath, Bath BA2 7AY, U.K.

Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan

WPI-Advanced Institute for Materials Research, Tohoku University, 2-2-1 Katahira, Aoba-ku, Sendai 980-8577, Japan

Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, U.K.

Diamond Light Source Ltd., Harwell Science & Innovation Campus, Didcot, Oxfordshire OX11 0DE, U.K.

Global E3 Institute and Department of Materials Science and Engineering, Yonsei University, Seoul 120-749, Korea

Funding

Engineering and Physical Sciences Research Council · European Research Council · Higher Education Funding Council for England · Science and Technology Facilities Council · Deutsche Forschungsgemeinschaft · Cambridge Overseas Trust · Seventh Framework Programme

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