Multiferroics by Rational Design: Implementing Ferroelectricity in Molecule‐Based Magnets

Pardo, Emilio; Train, Cyrille; Liu, Hongbo; Chamoreau, Lise‐Marie; Dkhil, Brahim; Boubekeur, Kamal; Lloret, Francesc; Nakatani, Keitaro; Tokoro, Hiroko; Ohkoshi, Shin‐ichi; Verdaguer, Michel

doi:10.1002/ange.201202848

Cited by 37 publications

(9 citation statements)

References 41 publications

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“…Nevertheless, they are the first oxalate‐based compounds in which organic dications are inserted, whereas dicationic coordination complexes were used previously to template the formation of 2D and, on a much wider scale, 3D oxalate‐based coordination networks. In comparison with previous cases,, the competition between coordination and hydrogen bonds did not hinder the formation of the 2D coordination network, but, as observed previously,[8b], it induced the corrugation of the layers because the Mn II centers are heptacoordinate owing to the coordination of an alcohol molecule. This unusual coordination influences the magnetic exchange parameter between the metal centers, though the switch from a ferromagnetic to an antiferromagnetic interaction observed in 4 was neither observed experimentally for 1 – 3 nor reproduced theoretically for 1 – 4 .…”

Section: Discussionsupporting

confidence: 70%

“…This contrasts with the “standard” oxalate‐based networks but was previously observed with other H‐bond‐active cations, which led to the distortion of the coordination network and even to reduced dimensionality of the coordination architecture or to isolated polynuclear complexes. [8b], , In the present cases, the implication of the oxygen atoms of the oxalate ligands in hydrogen bonds weakens their coordination ability towards the Mn II centers and allows the coordination of an extra monodentate ligand available in solution, for example, a methanol molecule.…”

Section: Resultsmentioning

confidence: 94%

“…Nevertheless, this coordination mode can be hindered if the coordination bonding has to compete with intermolecular interactions of comparable magnitude. Accordingly, the use of counterions with H‐bonding abilities has led to the synthesis of compounds in which the topology of the coordination polymer is different , . For the most severe competition, a reduction of the dimensionality to form one‐dimensional compounds or discrete polymetallic entities has been observed .…”

Section: Introductionmentioning

confidence: 99%

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Amidinium‐Containing 2D [MnCr] Dimetallic Oxalate‐Based Networks – The Influence on Structure and Magnetism Explored by Combining Experience and Theory

et al. 2016

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Three X2+ bisamidinium dications are inserted into oxalate‐based dimetallic [MnCr] compounds of formula X[MnII(CH3OH)CrIII(ox)3]2·nS [X2+ = C14N4H202+ (cation A2+, compound 1), C14O2N4H202+ (cation B2+, compound 2), C16N4H242+ (cation C2+, compound 3); n = 4 (1–2), 2 (3); S = CH3OH (1–2), CH3CN (3); ox = oxalate]. Single‐crystal X‐ray analysis of 1–3 reveals that Mn–Cr oxalate‐bridged dimetallic coordination networks form corrugated two‐dimensional (2D) layers based on heptacoordinate MnII ions surrounded by six oxygen atoms from three bis‐bidentate oxalate ions and one oxygen atom from a coordinated methanol molecule. In 1–3, the observed coordination environments of the MnII ions are close to capped trigonal prismatic (CTPR‐7) according to continuous shape measurements (CSM). Curie–Weiss temperatures of 0.62, 0.42, and 0.54 K for 1–3, respectively, were deduced from the magnetic susceptibility measurements and reveal dominant ferromagnetic exchange interactions. Ab initio calculations up to the DDCI‐2 level were performed on [MnCr] dimeric units and allowed the evaluation of the exchange interactions in 1–3.

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Section: Discussionsupporting

confidence: 70%

Section: Resultsmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

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Amidinium‐Containing 2D [MnCr] Dimetallic Oxalate‐Based Networks – The Influence on Structure and Magnetism Explored by Combining Experience and Theory

et al. 2016

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“…The elaboration of molecular compounds with multiple properties remains an exciting and complex challenge for both chemists and physicists. Ferroelectricity in molecular magnets1 or single molecule magnets2 (SMMs), spin crossover (SCO) in molecular magnets,3 magnetic and electric bistability in chiral magnets,4 and electronic conductivity and chirality in polymeric magnets5 are topical examples.…”

Section: Introductionmentioning

confidence: 99%

Unprecedented Sensitization of Visible and Near‐Infrared Lanthanide Luminescence by Using a Tetrathiafulvalene‐Based Chromophore

Feng

Pointillart

Guennic

et al. 2014

Chemistry An Asian Journal

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Ligand L was synthesized and then coordinated to [Ln(hfac)3]⋅2 H2O (Ln(III)=Tb, Dy, Er; hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion) and [Ln(tta)3]⋅2 H2O (Ln(III)=Eu, Gd, Tb, Dy, Er, Yb; tta(-)=2-thenoyltrifluoroacetonate) to give two families of dinuclear complexes [Ln2(hfac)6(L)]⋅C6H14 and [Ln2(tta)6(L)]⋅2 CH2Cl2. Irradiation of the ligand at 37,040 cm(-1) and 29,410 cm(-1) leads to tetrathiafulvalene-centered and 2,6-di(pyrazol-1-yl)-4-pyridine-centered fluorescence, respectively. The ligand acts as an organic chromophore for the sensitization of the infrared Er(III) (6535 cm(-1)) and Yb(III) (10,200 cm(-1)) luminescence. The energies of the singlet and triplet states of L are high enough to guarantee an efficient sensitization of the visible Eu(III) luminescence (17,300-14,100 cm(-1)). The Eu(III) luminescence decay can be nicely fitted by a monoexponential function that allows a lifetime estimation of (0.49±0.01) ms. Finally, the magnetic and luminescence properties of [Yb2(hfac)6(L)]⋅C6H14 were correlated, which allowed the determination of the crystal field splitting of the (2)F(7/2) multiplet state with M(J)=±1/2 as ground states.

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“…In 2009, Jain et al reported a multiferroic behavior in a family of perovskite MOFs8. This finding has stimulated considerable experimental and theoretical efforts to search for new multiferroic materials in MOFs910112324252627282930. However, the cross coupling between magnetic and electric orders in MOFs, an extremely important feature required for applications, has not been verified in previous studies, which has casted doubt on the promise of organic multiferroics.…”

mentioning

confidence: 99%

Cross coupling between electric and magnetic orders in a multiferroic metal-organic framework

Tian

Stroppa²,

Chai

et al. 2014

Sci Rep

189

181

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The coexistence of both electric and magnetic orders in some metal-organic frameworks (MOFs) has yielded a new class of multiferroics beyond inorganic materials. However, the coupling between two orders in multiferroic MOFs has not been convincingly verified yet. Here we present clear experimental evidences of cross coupling between electric and magnetic orders in a multiferroic MOF [(CH3)2NH2]Fe(HCOO)3 with a perovskite structure. The dielelectric constant exhibit a hump just at the magnetic ordering temperature TN. Moreover, both the direct (magnetic field control of dielectric properties) and converse (electric field control of magnetization) magnetoelectric effects have been observed in the multiferroic state. This work opens up new insights on the origin of ferroelectricity in MOFs and highlights their promise as magnetoelectric multiferroics.

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Multiferroics by Rational Design: Implementing Ferroelectricity in Molecule‐Based Magnets

Cited by 37 publications

References 41 publications

Amidinium‐Containing 2D [MnCr] Dimetallic Oxalate‐Based Networks – The Influence on Structure and Magnetism Explored by Combining Experience and Theory

Amidinium‐Containing 2D [MnCr] Dimetallic Oxalate‐Based Networks – The Influence on Structure and Magnetism Explored by Combining Experience and Theory

Unprecedented Sensitization of Visible and Near‐Infrared Lanthanide Luminescence by Using a Tetrathiafulvalene‐Based Chromophore

Cross coupling between electric and magnetic orders in a multiferroic metal-organic framework

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