Crossover between Tilt Families and Zero Area Thermal Expansion in Hybrid Prussian Blue Analogues

Angewandte Chemie
Anthony E Phillips, A Dominic Fortes

Abstract

Materials in the family of Prussian blue analogues (C3 H5 N2 )2 K[M(CN)6 ], where C3 H5 N2 is the imidazolium ion and M=Fe, Co, undergo two phase transitions with temperature; at low temperatures the imidazolium cations have an ordered configuration (C2/c), while in the intermediate- and high-temperature phases (both previously reported as R3‾m ) they are dynamically disordered. We show from high-resolution powder neutron diffraction data that the high-temperature phase has zero area thermal expansion in the ab-plane. Supported by Landau theory and single-crystal X-ray diffraction data, we re-evaluate the space group symmetry of the intermediate-temperature phase to R3‾ . This reveals that the low-to-intermediate temperature transition is due to competition between two different tilt patterns of the [M(CN)6 ]3- ions. Controlling the relative stabilities of these tilt patterns offers a potential means to tune the exploitable electric behaviour that arises from motion of the imidazolium guest.

References

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Citations

Apr 9, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Magdalena RokGrażyna Bator
Mar 20, 2019·Chemical Communications : Chem Comm·Zhanning LiuXianran Xing
Oct 7, 2020·Chemical Communications : Chem Comm·Anthony E PhillipsFranz Demmel

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