Electric Control of Magnetization and Interplay between Orbital Ordering and Ferroelectricity in a Multiferroic Metal–Organic Framework

Stroppa, Alessandro; Jain, Prashant K.; Barone, Paolo; Marsman, Martijn; Perez-Mato, J. M.; Cheetham, Anthony K.; Kroto, Harold W.; Picozzi, Silvia

doi:10.1002/anie.201101405

Cited by 264 publications

(254 citation statements)

References 33 publications

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“…13,14 Cross-coupling between the electric and magnetic orders has been observed, [15][16][17][18] and low temperature phase separation leads to quantum tunneling of the magnetization. 19 Figure 1 displays the crystal structure of this compound and summarizes the aforementioned energy scales.…”

Section: Introductionmentioning

confidence: 99%

Magnetic field-temperature phase diagram of multiferroic [(CH3)2NH2]Mn(HCOO)3<

et al. 2017

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We combined pulsed field magnetization and first principles spin density calculations to reveal the magnetic field-temperature phase diagram and spin state character in multiferroic [(CH3)2NH2]Mn(HCOO)3. Despite similarities with the rare earth manganites, the phase diagram is analogous to other Mn-based quantum magnets with a 0.31 T spin flop, a 15.3 T transition to the fully polarized state, and short range correlations that persist above the ordering temperature. The experimentally accessible saturation field opens the door to exploration of the high field phase.

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Section: Introductionmentioning

confidence: 99%

Magnetic field-temperature phase diagram of multiferroic [(CH3)2NH2]Mn(HCOO)3<

et al. 2017

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“…Although the mechanisms of these magnetic and electric orderings are considered to be independent, recent studies show signifi cant cross-coupling (ME effect). 23 This could be explained by the electric-fi eld manipulation of the orientation of H-bonding between the cationic guest molecules with the framework. 24 -27 However, due to the low transition temperatures for electrical ordering (160-185 K) and magnetic behavior (8-36 K), 21 the ME coupling effects are limited to low transition temperatures (up to 19 K).…”

Section: Multiferroic Behaviormentioning

confidence: 99%

Guest molecules as a design element for metal–organic frameworks

2016

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The well-known synthetic versatility of metal-organic frameworks (MOFs) is rooted in the ability to predict the metal-ion coordination geometry and the vast possibilities to use organic chemistry to modify the linker groups. However, the use of molecules occupying the pores as a component of framework design has been largely ignored. Recent reports show that the presence of these so-called "guests" can have dramatic effects, even when they are a seemingly innocuous species such as water or polar solvents. We term these guests "noninnocent" when their presence alters the MOF in such a way as to create a new material with properties different from the MOF without the guests. Advantages of using guest molecules to impart new properties to MOFs include the relative ease of introducing new functionalities, the ability to modify the material properties at will by removing the guest or inserting different ones, and avoidance of the diffi culties associated with synthesizing new frameworks, which can be challenging even when the basic topology remains constant. In this article, we describe the "Guest@MOF" concept and provide examples illustrating its potential as a new MOF design element.

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“…1]. 28,32,33 In particular, we anticipated that substitution on the Cu site by JT-inactive cations (i.e., Mn, Zn, Mg; note Cd gives a different structure type 28,34 ) might be expected to reduce the length-scale of polar order, and-if clustering were found to occur-then favour the formation of PNRs in Cu dilute compositions.Moreover, a computational study of [Gua]Mn 0.5 Cu 0.5 (HCOO) 3 has recently suggested strong enhancement in both polarization and magnetization relative to the Mn-and Cu-containing end-members. 35 Our focus here is on the synthesis and structural characterisation of three [Gua]Cu x M 1−x (HCOO) 3 families (M = Mn, Zn, Mg) rather than their dielectric behaviour, (although we anticipate our results will have strong implications for the latter).…”

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confidence: 99%

“…Hence [Gua]Cu(HCOO) 3 (right) is polar, with the orientation of polarization a function of the phase of collective JT order. 32 analysis of infrared (IR) spectroscopy data, we determine the experimental distribution of neighbouring cation pairs as a function of composition. We use these data to drive reverse Monte Carlo 38 (RMC) refinements of cation distributions, which in turn reveal nanodomain formation precisely of the type observed in conventional relaxor ferroelectrics such as PMN-PT.…”

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Compositional nanodomain formation in hybrid formate perovskites

et al. 2017

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We report the synthesis and structural characterisation of three mixed-metal formate perovskite families [C(NH 2 ) 3 ]M 1−x Cu x (HCOO) 3 (M = Mn, Zn, Mg). Using a combination of infrared spectroscopy, non-negative matrix factorization, and reverse Monte Carlo refinement, we show that the Mn-and Zn-containing compounds support compositional nanodomains resembling the polar nanoregions of conventional relaxor ferroelectrics. The M = Mg family exhibits a miscibility gap that we suggest reflects the limiting behaviour of nanodomain formation.Compositional heterogeneity is an essential ingredient in a number of important classes of functional materials. 1 Arguably the clearest example is that of the relaxor ferroelectrics, such as (1 − x)Pb(Mg 1/3 Nb 2/3 )O 3 -xPbTiO 3 (PMN-PT): 2 here an inhomogeneous distribution of B-site cations allows the formation of polar nanoregions (PNRs), 3-5 the collective motion of which is responsible for the giant electromechanical response observed and exploited experimentally. 6,7 Recently, the same ideas have been extended to relaxor ferromagnets, 8 which are in turn conceptually related to cluster spin glasses, 9 known for their exotic magnetic memory effects. 10 Likewise, in some porous metal-organic frameworks (MOFs), inhomogeneous vacancy distributions 11 affect gas uptake 12 via a mechanism that is analogous to ion conduction pathways in compositionally-heterogeneous solid-oxide fuel-cell materials. 13 From a materials design perspective, the existence of nanoscale compositional inhomogeneities relies on a delicate balance of interaction strengths at the atomic scale. If the interaction between [18][19][20] It was in this context that we sought to explore cation distributions in the mixed-metal formate perovskites [Gua]Cu x M 1−x (HCOO) 3 (Gua + = C(NH 2 ) + 3 ; M = Mn, Zn, Mg). It has been known for some time that many formate perovskites show relaxor-like dielectric behaviour, [21][22][23] which is usually associated with glassy dynamics of the organic (A-site) cation. 24,25 Indeed a recent 13 C NMR study of [(CH 3 ) 2 NH 2 ]Zn(HCOO) 3 even demonstrated the spontaneous formation of fluxional PNRs during the onset of ferroelectric order. 26 By contrast, the exploration of mixed-metal formate perovskites is rather less well developed. 27-31 Our focus here on the [Gua]M(HCOO) 3 family is motivated by the link in this particular system between polarization and cooperative Jahn-Teller (JT) order for M = Cu [ Fig. 1]. 28,32,33 In particular, we anticipated that substitution on the Cu site by JT-inactive cations (i.e., Mn, Zn, Mg; note Cd gives a different structure type 28,34 ) might be expected to reduce the length-scale of polar order, and-if clustering were found to occur-then favour the formation of PNRs in Cu dilute compositions.Moreover, a computational study of [Gua]Mn 0.5 Cu 0.5 (HCOO) 3 has recently suggested strong enhancement in both polarization and magnetization relative to the Mn-and Cu-containing end-members. 35 Our focus here is on the synthesis and structural char...

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Electric Control of Magnetization and Interplay between Orbital Ordering and Ferroelectricity in a Multiferroic Metal–Organic Framework

Cited by 264 publications

References 33 publications

Magnetic field-temperature phase diagram of multiferroic [(CH3)2NH2]Mn(HCOO)3<

Magnetic field-temperature phase diagram of multiferroic [(CH3)2NH2]Mn(HCOO)3<

Guest molecules as a design element for metal–organic frameworks

Compositional nanodomain formation in hybrid formate perovskites

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