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Hybrid Improper Ferroelectricity in a Multiferroic and Magnetoelectric Metal‐Organic Framework

Authors: Stroppa; Aa; Barone; Pa; Jain; Pb; PerezMato; +3 Authors

Hybrid Improper Ferroelectricity in a Multiferroic and Magnetoelectric Metal‐Organic Framework

Abstract

There is great interest in hybrid organic-inorganic materials such as metal-organic frameworks (MOFs). The compounds [C(NH$_{2}$)$_{3}$]M(HCOO)$_{3}$, where M=Cu$^{2+}$ or Cr$^{2+}$ are Jahn-Teller (JT) active ions, are MOF with perovskite topology which crystallizes in polar space group Pna2$_{1}$. In inorganic compounds, octahedral tilting and Jahn-Teller structural distortions are usually non-polar distortions. However, in this MOF cooperative interactions between the antiferro-distortive distortions of the framework and the C(NH2)$_{3}$ organic cation via hydrogen bonding breaks the inversion symmetry and induces a ferroelectric polarization.[Angew. Chem. Int. Ed. 50, 5847, 2011] Our ab-initio study supports the picture of an orbital-order-induced ferroelectricity, a rare example of dipolar ordering caused by electronic degrees of freedom. The switching of polarization direction implies the reversal of the weak ferromagnetic component. The microscopic mechanism in this JT-based MOF with ABX$_{3}$ perovskite structure displays a Hybrid Improper Ferroelectric (HIF) state, arising from a trilinear coupling between different structural deformations that comprise tilting, rotations and Jahn-Teller distortions of both the BX$_{3}$ framework and the organic cation at the A sites. Since these distortion modes in perovskite-inorganic compounds usually freeze-in at elevated temperatures, the trilinear coupling in MOF compounds may provide an interesting route towards high-temperature multiferroicity. These results offer an important starting point for tailoring multiferroic properties in this emerging class of materials for various technological applications. In particular, the high tunability of the ferroelectric polarization by means of the modification of the organic A cation has been recently shown[J. Am. Chem. Soc. 135 18126 (2013)]

Country
Italy
Keywords

jahn-teller, magnetoelectrics, multiferroics, pseudo-rotation, hybrid improper ferroelectrics, hybrid improper ferroelectrics; jahn-teller; magnetoelectrics; metal-organic frameworks; multiferroics; pseudo-rotation;, metal-organic frameworks

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
306
Top 1%
Top 1%
Top 0.1%
bronze