Pressure Effect on Order-Disorder Ferroelectric Transition in a Hydrogen-Bonded Metal-Organic Framework

J Phys Chem Lett. 2020 Nov 19;11(22):9566-9571. doi: 10.1021/acs.jpclett.0c02943. Epub 2020 Oct 29.

Abstract

Perovskite-like ABX3 metal-organic frameworks (MOFs) have gathered great interest due to their intriguing chemical and physical properties, including their magnetism, ferroelectricity, and multiferroicity. Pressure is an effective thermal parameter in tuning related properties in MOFs due to the adjustable organic framework. Though spectrum experiments have been made on the structural evolution during decompression, there is a lack of electrical studies on the order-disorder ferroelectric transition in the metal-organic frameworks under pressure. In this work, we use a static pyroelectric current measurement, a dynamic dielectric method combined with a Raman scattering technique with applying in situ pressure, to explore the order-disorder ferroelectric transition in [(CH3)2NH2]Co(HCOO)3. The ferroelectric transition vanishes around the external pressure of 1.6 GPa, emerging with a new paraelectric phase. Another phase transition was observed at 6.32 GPa, mainly associated with the distortive transition of DMA+ cations. A phenomenological theory of ferroelectricity vanishing at 1.6 GPa for [(CH3)2NH2]Co(HCOO)3 is also discussed. Our study gives a comprehensive understanding in the pressure tuning of ferroelectric properties in hybrid inorganic-organic materials.