M. Sánchez-Andújar

Characterization of the Order−Disorder Dielectric Transition in the Hybrid Organic−Inorganic Perovskite-Like Formate Mn(HCOO)3[(CH3)2NH2]

We have found that the hybrid organic-inorganic perovskite-like formate Mn(HCOO)(3)[(CH(3))(2)NH(2)] shows a dielectric transition around 190 K. According to single crystal X-ray diffraction, the compound shows rhombohedral symmetry at room temperature and monoclinic symmetry at low temperature (100 K), and the main difference between both structures is that the (CH(3))(2)NH(2)(+) (DMA) cations are disordered in the high temperature phase but cooperatively ordered in the low temperature one. The vibrational spectra of this compound reveal that significant changes take place in the vibrations ascribed to the DMA cation (changes in the frequency of certain vibrations, splitting of particular vibrations, and changes in the intensities), while no significant changes have been observed in those attributed to the formate anion. On the basis of all this information, we attribute the origin of the dielectric transition to the dynamics of the DMA cations: above 190 K these cations can rotate inside the cubooctahedral cavity created by the [Mn(HCOO)(3)](-) framework, while for lower temperatures such rotation gets frozen, and their cooperative arrangement inside the cavities give rise to the observed dielectric transition.

Magnetic ordering-induced multiferroic behavior in [CH3NH3][Co(HCOO)3] metal-organic framework.

We present the first example of magnetic ordering-induced multiferroic behavior in a metal-organic framework magnet. This compound is [CH3NH3][Co(HCOO)3] with a perovskite-like structure. The A-site [CH3NH3](+) cation strongly distorts the framework, allowing anisotropic magnetic and electric behavior and coupling between them to occur. This material is a spin canted antiferromagnet below 15.9 K with a weak ferromagnetic component attributable to Dzyaloshinskii-Moriya (DM) interactions and experiences a discontinuous hysteretic magnetic-field-induced switching along [010] and a more continuous hysteresis along [101]. Coupling between the magnetic and electric order is resolved when the field is applied along this [101]: a spin rearrangement occurs at a critical magnetic field in the ac plane that induces a change in the electric polarization along [101] and [10-1]. The electric polarization exhibits an unusual memory effect, as it remembers the direction of the previous two magnetic-field pulses applied. The data are consistent with an inverse-DM mechanism for multiferroic behavior.

Room-temperature polar order in [NH4][Cd(HCOO)3]--a hybrid inorganic-organic compound with a unique perovskite architecture.

We report on the hybrid inorganic-organic ammonium compound [NH4][Cd(HCOO)3], which displays a most unusual framework structure: instead of the expected 4(9)·6(6) topology, it shows an ABX3 perovskite architecture with the peculiarity and uniqueness (among all the up-to-date reported hybrid metal formates) that the Cd ions are connected only by syn-anti formate bridges, instead of anti-anti ones. This change of the coordination mode of the formate ligand is thus another variable that can provide new possibilities for tuning the properties of these versatile functional metal-organic framework materials. The room-temperature crystal structure of [NH4][Cd(HCOO)3] is noncentrosymmetric (S.G.: Pna21) and displays a polar axis. DFT calculations and symmetry mode analysis show that the rather large polarization arising from the off-center shift of the ammonium cations in the cavities (4.33 μC/cm(2)) is partially canceled by the antiparallel polarization coming from the [Cd(HCOO)3](-) framework, thus resulting in a net polarization of 1.35 μC/cm(2). As shown by second harmonic generation studies, this net polarization can be greatly increased by applying pressure (Pmax = 14 GPa), an external stimulus that, in turn, induces the appearance of new structural phases, as confirmed by Raman spectroscopy.

First-order structural transition in the multiferroic perovskite-like formate [(CH3)2NH2][Mn(HCOO)3]

In this work we explore the overall structural behaviour of the [(CH3)2NH2][Mn(HCOO)3] multiferroic compound across the temperature range where its ferroelectric transition takes place by means of calorimetry, thermal expansion measurements and variable temperature powder and single crystal X-ray diffraction. The results clearly prove the presence of a structural phase transition at Tt ~ 187 K (the temperature at which the dielectric transition occurs) that involves a symmetry change from Rc to Cc, twinning of the crystals, a discontinuous variation of the unit cell parameters and unit cell volume, and a sharp first-order-like anomaly in the thermal expansion. In addition, the calorimetric results show a 3-fold order–disorder transition. The calculated pressure dependence of the transition temperature is rather large (dTt/dP = 4.6 ± 0.1 K kbar−1) in that it should be feasible to shift it to room temperature under adequate thermodynamic conditions, for instance by application of an external pressure.

Coexistence of magnetic and electrical order in the new perovskite-like (C3N2H5)[Mn(HCOO)3] formate

In this work we further the structural characterization of the recently discovered (C3N2H5)[Mn(HCOO)3] metal–organic framework with perovskite-like structure, and we present its magnetic and dielectric properties up to 350 K. At low temperature, the C3N2H5+ imidazolium cations, that sit oblique within the cavities of the [Mn(HCOO)3]− framework structure, show a cooperative order resulting in an antiparallel arrangement of their electrical dipole moments. Very interestingly, it is only above 220 K that thermal energy seems to be able to break this antiferroelectric order, resulting in a linear increase of its dielectric constant with temperature. In addition, this Mn(II) compound is antiferromagnetic below TN = 9 K, with a slightly non-collinear arrangement of its magnetic moments, yielding to a weak ferromagnetism. Therefore, this is a new multiferroic material which exhibits coexistence of magnetic and electric ordering.

Role of temperature and pressure on the multisensitive multiferroic dicyanamide framework [TPrA][Mn(dca)(3)] with perovskite-like structure

A multistimuli response to temperature and pressure is found in the hybrid inorganic-organic perovskite-like [TPrA][Mn(dca)3] compound, which is related to a first-order structural phase transition near room temperature, Tt ≈ 330 K. This phase transition involves a transformation from room temperature polymorph I, with the noncentrosymmetric space group P4̅21c, to the high temperature polymorph II, with the centrosymmetric space group I4/mcm, and it implies ionic displacements, order-disorder phenomena, and a large and anisotropic thermal expansion (specially along the c-axis). As a consequence, [TPrA][Mn(dca)3] exhibits a dielectric anomaly, associated with the change from a cooperative to a noncooperative electric behavior (antiferroelectric (AFE)-paraelectric (PE) transition). The former implies an AFE distribution of electric dipoles in polymorph I, related to the described off-shift of the apolar TPrA cations and the order-disorder of the polar dca ligands mechanisms, that are different from those reported, up to now, for others perovskite-type hybrid compounds. Such cooperative electric order, below Tt ≈ 330 K, coexisting with long-range antiferromagnetic ordering below T = 2.1 K render the [TPrA][Mn(dca)3] a new type-I multiferroic material. In addition, the obtained experimental results reveal that this compound is also a multistimuli-responsive material, with a very large sensitivity toward temperature and applied external pressure, δTt/δP ≈ 24 K kbar(-1), even for small values of pressure (P < 2 kbar). Therefore, this material opens up a potential interest for future technological applications, such as temperature/pressure sensing.

Multiple phase and dielectric transitions on a novel multi-sensitive [TPrA][M(dca)3] (M: Fe2+, Co2+ and Ni2+) hybrid inorganic–organic perovskite family

The hybrid inorganic–organic [TPrA][M(dca)3] (M: Fe2+, Co2+ and Ni2+) compounds, where TPrA is the tetrapropylammonium cation and dca is the dicyanamide anion, are unique multi-sensitive compounds that display multiple phases and dielectric transitions. These materials exhibit up to three first-order structural transitions (between the polymorphs I, Ia, Ib and II) associated with the same number of dielectric transitions in the temperature range of 210–360 K. The mechanisms responsible for these dielectric responses are found to be novel within the hybrid perovskites, involving ionic displacements of the A-site cations (TPrA) and order/disorder processes of the X anions (dca). In addition, the phase transitions and dielectric transition temperatures can be tuned by applying external hydrostatic pressure or by inducing internal pressure by modifying the tolerance factor through ionic substitution in the B-sites. This multi-sensitive response towards temperature, external and internal pressure opens up promising technological applications for this family of materials, such as dielectric transductors or multistimuli-sensors, whose response can be modulated in a wide range of temperatures and pressures.

Coexistence of Three Ferroic Orders in the Multiferroic Compound [(CH3)4N][Mn(N3)3] with Perovskite‐Like Structure

The perovskite azido compound [(CH3 )4 N][Mn(N3 )3 ], which undergoes a first-order phase change at Tt =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 [MnN6 ] octahedral as well as order/disorder and off-center shifts of the [(CH3 )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, [(CH3 )4 N][Mn(N3 )3 ] is a singular material in which three ferroic orders coexist even above room temperature.

Synthesis, characterization, magnetism and transport properties of Nd1−xSrxCoO3 perovskites

Abstract We have prepared polycrystalline, single-phase Nd1−xSrxCoO3 materials (0≤x≤0.40) using the nitrate decomposition method and we have studied how their structural, magnetic and transport properties change upon Sr2+ doping. In this context we find that these series of compounds crystallize in GdFeO3-type perovskite structures whose cell volume increases as x gets higher. From the magnetic point of view, this doping makes the materials evolve towards a ferromagnetic behavior as x increases, so that for x>0.20 the samples are already ferromagnetic below a Tc∼225 K. Also, their electrical conductivity progressively increases with x. Nevertheless the materials remain semiconducting for x≤0.30 and only the sample with x=0.40 displays a M–I transition as a function of temperature (TMI∼160 K).

Role of the magnetic ordering on the dielectric response of M2V2O7 (M = Co and Cu) divanadates

We have synthesized two divanadates M2V2O7 (M2+ = Co2+ and Cu2+), that are known to show different and complex magnetic arrangements at low temperatures and have studied their dielectric behavior. We have observed a change in the slope of the dielectric constant at the magnetic transition temperature, result which confirms the existence of magnetodielectric coupling in these two divanadates. The origin of the magnetodielectric coupling seems to be different in the Cu- and Co-compounds, although in both cases it is related to their frustrated magnetic arrangement. In Cu2V2O7, the dielectric anomaly arises from a spin canting due to the antisymmetric exchange which is allowed by structural symmetry. In the Co-divanadate, the structural symmetry does not allow antisymmetric exchange but the compound shows correlation between the behavior of the dielectric constant and inverse magnetization, which points to a dependence of its electrical polarization with the pair correlation function of neighboring magnetic ...