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Coexistence of Three Ferroic Orders in the Multiferroic Compound [(CH 3 ) 4 N][Mn(N 3 ) 3 ] with Perovskite‐Like Structure

2016; Wiley; Volume: 22; Issue: 23 Linguagem: Inglês

10.1002/chem.201503445

1521-3765

L. C. Gómez-Aguirre, Breogán Pato‐Doldán, Alessandro Stroppa, Li‐Ming Yang, Thomas Frauenheim, J. Mira, S. Yáñez‐Vilar, Ramón Artiaga, Socorro Castro‐García, Manuel Sánchez‐Andújar, M. A. Señarís‐Rodríguez,

Solid-state spectroscopy and crystallography

Abstract The perovskite azido compound [(CH 3 ) 4 N][Mn(N 3 ) 3 ], which undergoes a first‐order phase change at T t =310 K with an associated magnetic bistability, was revisited in the search for additional ferroic orders. The driving force for such structural transition is multifold and involves a peculiar cooperative rotation of the [MnN 6 ] octahedral as well as order/disorder and off‐center shifts of the [(CH 3 ) 4 N] + cations and bridging azide ligands, which also bend and change their coordination mode. According to DFT calculations the latter two give rise to the appearance of electric dipoles in the low‐temperature (LT) polymorph, the polarization of which nevertheless cancels out due to their antiparallel alignment in the crystal. The conversion of this antiferroelectric phase to the paraelectric phase could be responsible for the experimental dielectric anomaly detected at 310 K. Additionally, the structural change involves a ferroelastic phase transition, whereby the LT polymorph exhibits an unusual and anisotropic thermal behavior. Hence, [(CH 3 ) 4 N][Mn(N 3 ) 3 ] is a singular material in which three ferroic orders coexist even above room temperature.