Multiferroic and thermal expansion properties of metal-organic frameworks

Ma, Yanying; Sun, Young

doi:10.1063/1.5137819

Cited by 29 publications

(21 citation statements)

References 74 publications

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“…Among different HOIPs, hybrid formate perovskites, e.g., A½MðHCOOÞ 3 with M ¼ Mn, Fe, Co, Ni, Zn, Mg, are very attractive as the formate group linker on the X site opens up the space to accommodate much larger varieties of organic A-site cations, e.g., ðCH 3 Þ 2 NH 2 , NH 3 NH 2 [6,7]. Several ferroelectric or antiferroelectric formates have been reported [8]. The structural transitions leading to ferroelectricity in these materials is of order-disorder type due to the disorder of the cation [1].…”

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confidence: 99%

Unusual Properties of Hydrogen-Bonded Ferroelectrics: The Case of Cobalt Formate

et al. 2022

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Hybrid organic-inorganic perovskites is a class of materials with diverse chemically tunable properties and outstanding potential for multifunctionality. We use first-principles simulations to predict room temperature ferroelectricity in a representative of the formate family, ½NH 2 NH 3 ½CoðHCOOÞ 3 . The ferroelectricity arises as a "by-product" of structural transition driven by the stabilization of the hydrogen bond. As a consequence the coupling with the electric field is relatively weak giving origin to large intrinsic coercive fields and making material immune to the depolarizing fields known for its detrimental role in nanoscale ferroelectrics. Insensitivity to the electric field and the intrinsic dynamics of the order-disorder transition in such material leads to the supercoercivity defined as significant increase in the coercive field with frequency. Room temperature polarization measurements provide further support for the predictions.

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confidence: 99%

Unusual Properties of Hydrogen-Bonded Ferroelectrics: The Case of Cobalt Formate

et al. 2022

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“…Furthermore, the spin-canted antiferromagnetic ordering transitions in [(CH 3 ) 2 NH 2 ][M(HCOO) 3 ] (M = Mn, Co, Ni, Fe, Cu) occur below 40 K (Ni: 35.6 K, Fe: 20 K, Co: 14.9 K, Mn: 8.5 K, Cu: 5.2 K) due to the metal ions within the framework skeletons, and the spin reorientation transitions in [(CH 3 ) 2 NH 2 ][M(HCOO) 3 ] (M = Co, Ni) occur at 13.1–14.3 K (Co: 13.1 K, Ni: 14.3 K) [ 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 ]. The effect of pressure on the structure and the electric and magnetic properties of [(CH 3 ) 2 NH 2 ][M(HCOO) 3 ] (M = Mg, Mn, Co, Zn, Cd) was investigated [ 37 , 47 , 54 , 55 , 56 ].…”

Section: Introductionmentioning

confidence: 99%

“…The ferroelectric transition temperature is the highest when M is Mg, because Mg 2+ is the hardest Lewis acid among them, leading to the strongest hydrogen bonds [35]. Furthermore, the spin-canted antiferromagnetic ordering transitions in [(CH 3 ) 2 [37,47,[54][55][56].…”

Section: Introductionmentioning

confidence: 99%

Elastic Properties and Energy Loss Related to the Disorder–Order Ferroelectric Transitions in Multiferroic Metal–Organic Frameworks [NH4][Mg(HCOO)3] and [(CH3)2NH2][Mg(HCOO)3]

Zhang¹,

Yu²,

Shen³

et al. 2021

Materials

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Elastic properties are important mechanical properties which are dependent on the structure, and the coupling of ferroelasticity with ferroelectricity and ferromagnetism is vital for the development of multiferroic metal–organic frameworks (MOFs). The elastic properties and energy loss related to the disorder–order ferroelectric transition in [NH4][Mg(HCOO)3] and [(CH3)2NH2][Mg(HCOO)3] were investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The DSC curves of [NH4][Mg(HCOO)3] and [(CH3)2NH2][Mg(HCOO)3] exhibited anomalies near 256 K and 264 K, respectively. The DMA results illustrated the minimum in the storage modulus and normalized storage modulus, and the maximum in the loss modulus, normalized loss modulus and loss factor near the ferroelectric transition temperatures of 256 K and 264 K, respectively. Much narrower peaks of loss modulus, normalized loss modulus and loss factor were observed in [(CH3)2NH2][Mg(HCOO)3] with the peak temperature independent of frequency, and the peak height was smaller at a higher frequency, indicating the features of first-order transition. Elastic anomalies and energy loss in [NH4][Mg(HCOO)3] near 256 K are due to the second-order paraelectric to ferroelectric phase transition triggered by the disorder–order transition of the ammonium cations and their displacement within the framework channels, accompanied by the structural phase transition from the non-polar hexagonal P6322 to polar hexagonal P63. Elastic anomalies and energy loss in [(CH3)2NH2][Mg(HCOO)3] near 264 K are due to the first-order paraelectric to ferroelectric phase transitions triggered by the disorder–order transitions of alkylammonium cations located in the framework cavities, accompanied by the structural phase transition from rhombohedral R3¯c to monoclinic Cc. The elastic anomalies in [NH4][Mg(HCOO)3] and [(CH3)2NH2][Mg(HCOO)3] showed strong coupling of ferroelasticity with ferroelectricity.

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“…Metal–organic frameworks (MOFs) containing metal ions bridged by organic linkers forms the hybrid structure, which could combine both merits from the properties of inorganic and organic building blocks within a single-phase compound. − In particular, MOFs with perovskite-like ABX 3 structure have been extensively studied in recent years due to their fascinating physical and chemical properties such as magnetic ordering, − ferroelectric (or antiferroelectric) ordering, quantum tunneling of magnetization, multiferroicity, − magnetoelectric (ME) effect, − and so on.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Bond Tuning of Magnetoelectric Coupling in Metal–Organic Frameworks

Liu

Zhai

et al. 2020

J. Phys. Chem. C

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The ordering of hydrogen bonds plays a vital role in breaking space inversion symmetry and inducing the paraelectric to ferroelectric phase transition in metal–organic frameworks (MOFs). Magnetic field control of electric polarization has been observed in some MOFs. However, little is known about the effect of hydrogen bonds on the magnetoelectric effect in MOFs. Here, we studied the hydrogen bond tuning of the magnetoelectric effect in the hybrid inorganic–organic materials [(CH3)2NH2]Mn(HCOO)3 and [(CH3)2NH2]Mn0.5Ni0.5(HCOO)3. Hydrogen bond energy is weakened by the substitution of Ni ions in [(CH3)2NH2]Mn(HCOO)3, revealed by the dielectric measurement and Raman spectra. Moreover, the hydrogen bond strength can tune the contributions of the electric polarization components from the DMA+ cation and HCOO– framework, inducing the positive and negative magnetoelectric coefficients in [(CH3)2NH2]Mn(HCOO)3 and [(CH3)2NH2]Mn0.5Ni0.5(HCOO)3, respectively. Our study gives a microscopic mechanism for understanding the hydrogen bond assisted magnetoelectric effect.

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Multiferroic and thermal expansion properties of metal-organic frameworks

Cited by 29 publications

References 74 publications

Unusual Properties of Hydrogen-Bonded Ferroelectrics: The Case of Cobalt Formate

Unusual Properties of Hydrogen-Bonded Ferroelectrics: The Case of Cobalt Formate

Elastic Properties and Energy Loss Related to the Disorder–Order Ferroelectric Transitions in Multiferroic Metal–Organic Frameworks [NH4][Mg(HCOO)3] and [(CH3)2NH2][Mg(HCOO)3]

Hydrogen Bond Tuning of Magnetoelectric Coupling in Metal–Organic Frameworks

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