Atypical Magnetic Behavior in the Incommensurate (CH3NH3)[Ni(HCOO)3] Hybrid Perovskite.

A plethora of temperature-induced phase transitions have been observed in (CH3NH3)[M(HCOO)3] compounds, where M is Co(II) or Ni(II). Among them, the nickel compound exhibits a combination of magnetic and nuclear incommensurability below Néel temperature. Despite the fact that the zero-field behavior has been previously addressed, here we study in depth the macroscopic magnetic behavior of this compound to unveil the origin of the atypical magnetic response found in it and in its parent family of formate perovskites. In particular, they show a puzzling magnetization reversal in the curves measured starting from low temperatures, after cooling under zero field. The first atypical phenomenon is the impossibility of reaching zero magnetization, even by nullifying the applied external field and even compensating it for the influence of the Earth's magnetic field. Relatively large magnetic fields are needed to switch the magnetization from negative to positive values or vice versa, which is compatible with a soft ferromagnetic system. The atypical path found in its first magnetization curve and hysteresis loop at low temperatures is the most noticeable feature. The magnetization curve switches from more than 1200 Oe from the first magnetization loop to the subsequent magnetization loops. A feature that cannot be explained using a model based on unbalanced pair of domains. As a result, we decipher this behavior in light of the incommensurate structure of this material. We propose, in particular, that the applied magnetic field induces a magnetic phase transition from a magnetically incommensurate structure to a magnetically modulated collinear structure.

Phase Transition, Dielectric Properties, and Ionic Transport in the [(CH3)2NH2]PbI3 Organic-Inorganic Hybrid with 2H-Hexagonal Perovskite Structure.

In this work, we focus on [(CH3)2NH2]PbI3, a member of the [AmineH]PbI3 series of hybrid organic-inorganic compounds, reporting a very easy mechanosynthesis route for its preparation at room temperature. We report that this [(CH3)2NH2]PbI3 compound with 2H-perovskite structure experiences a first-order transition at ≈250 K from hexagonal symmetry P63/mmc (HT phase) to monoclinic symmetry P21/c (LT phase), which involves two cooperative processes: an off-center shift of the Pb2+ cations and an order-disorder process of the N atoms of the DMA cations. Very interestingly, this compound shows a dielectric anomaly associated with the structural phase transition. Additionally, this compound displays very large values of the dielectric constant at room temperature because of the appearance of a certain conductivity and the activation of extrinsic contributions, as demonstrated by impedance spectroscopy. The large optical band gap displayed by this material (Eg = 2.59 eV) rules out the possibility that the observed conductivity can be electronic and points to ionic conductivity, as confirmed by density functional theory calculations that indicate that the lowest activation energy of 0.68 eV corresponds to the iodine anions, and suggests the most favorable diffusion paths for these anions. The obtained results thus indicate that [(CH3)2NH2]PbI3 is an electronic insulator and an ionic conductor, where the electronic conductivity is disfavored because of the low dimensionality of the [(CH3)2NH2]PbI3 structure.

Liquid self-diffusion of H2O and DMF molecules in Co-MOF-74: molecular dynamics simulations and dielectric spectroscopy studies.

In this work we use molecular dynamics simulations to study the diffusion of N,N-dimethylformamide (DMF) and H2O as a function of temperature within the well-known metal-organic framework Co2(dobdc)·[G] (G = 2DMF·1H2O), also known as Co-MOF-74. The molecular dynamics simulations show that the diffusivity of guest molecules, which is almost negligible at low temperatures (T < 200 K), increases in the range of 200 < T (K) < 400 up to 3 and 4 orders of magnitude for DMF and H2O, respectively. This molecular diffusion can be easily detected by dielectric spectroscopy as it gives rise to extrinsic interfacial polarization effects that result in an apparent "colossal" dielectric constant at room temperature, εr' ∼ 42 000 (T = 300 K, ν = 10 Hz). Furthermore, the measured dielectric constant exhibits a thermal dependence similar to that of the diffusion coefficient, revealing the parallelism of the dielectric response and the molecular diffusion as a function of temperature. These results highlight: (a) the great utility of the fast and non-destructive dielectric and impedance spectroscopy techniques for the study and detection of the molecular transport of small polar molecules within porous metal-organic frameworks and related materials; (b) the peculiarity and uniqueness of MOF materials with "medium" size nanopores containing guest molecules as they are solid materials in which the guest molecules display a liquid state-like behaviour close to room temperature; and

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.

Near room temperature dielectric transition in the perovskite formate framework [(CH3)2NH2][Mg(HCOO)3].

We report that the hybrid organic-inorganic compound [(CH3)2NH2][Mg(HCOO)3] shows a marked dielectric transition around Tt∼ 270 K, associated to a structural phase transition from SG R3[combining macron]c (centrosymmetric) to Cc (non-centrosymmetric). This is the highest Tt reported so far for a perovskite-like formate that is thus a promising candidate to display electric order very close to room temperature.

Characterization of the order-disorder dielectric transition in the hybrid organic-inorganic perovskite-like formate Mn(HCOO)(3)[(CH(3))(2)NH(2)].

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.