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In this work, we introduce a new family of barocaloric hybrid organic-inorganic compounds with colossal barocaloric effects. The here reported hybrid materials, [(CH3)3(CH2Cl)N]FeCl4 and [(CH3)3S]FeCl4, exhibit a molecular structure composed by discrete inorganic anions and organic cations with weak elestrostatic interactions. Our calorimetric studies reveal colossal barocaloric effects of similar magnitude than organic plastic crystals (ΔS > 100 J K-1 kg-1) near room temperature and under smaller pressures (p ≤ 1000 bar), which leads to higher barocaloric strengths. Furthermore, these materials exhibit densities similar to barocaloric hybrid perovskites enhancing the volumetric barocaloric effects (ΔS ~ 200 J K-1 l-1), which could provide more compact cooling devices. Therefore, the colossal values of the mass and volumetric barocaloric effects and large barocaloric strength, in addition to the low working pressure and near-room-temperature operation, offer a new family of compounds to further explore in the search for improved barocaloric materials.

In this work, we report a new halometallate [(CH3)3S][FeCl4] with plastic crystal behaviour as a new material for multi-energy storage. This material undergoes a first-order solid-solid plastic crystal phase transition near room temperature with a relatively large latent heat (~40 kJ kg-1) and an operational temperature for storing and releasing thermal energy between 42 oC (315 K) and 29 oC (302 K), very appropriate for solar thermal energy storage. In addition, the dielectric, magnetization and electron spin resonance studies reveal that this material exhibits multifunctional properties with temperature-induced reversible changes in its dielectric, conducting and magnetic behaviour associated with the phase transition. Also, the dielectric permitivity increases sharply up to 5 times when inducing the phase transition, which can be exploited to store electric energy into a capacitor. Therefore, [(CH3)3S][FeCl4] is a very interesting compound with coexistence of multifunctional properties that can be useful for both solar thermal and electric energy storage.

In large quantities, water is detrimental to lead halide perovskite solar cells, mainly because of the decomposition of the perovskite layer. In contrast, the presence of small quantities of water has been observed to play a key role in the crystallization of the perovskite and in the performance of the corresponding devices. However, the exact role of water during the operation of perovskite solar cells is still under debate. In this paper, impedance spectroscopy is used to analyze the changes produced by environmental humidity in the electronic properties of methylammonium lead triiodide perovskite. Our results show that water absorbed from environmental humidity induces a huge increase in the capacitance of this material. This capacitance can reach values as large as the accumulation capacitance found in devices based on perovskite, which is responsible for the characteristic large hysteresis observed between forward and reverse J–V curves. In parallel to this outstanding rise of the capacitance, water absorption produces a significant rise of the conductivity, in agreement with previous reports in the literature. An activation energy of 0.52 eV is found for electronic transport, a value in line with the activation energy of ionic transport found in the literature, which suggests ambipolar diffusion as the transport mechanism that links these two phenomena.

We have prepared two new lead halides with the novel general formula of DMA7Pb4X15 (DMA = [(CH3)2NH2]+ and X = Cl– or Br–) by using an easy route under mild conditions at room temperature. These compounds exhibit an unprecedented crystal structure, are formed by layers of distorted [PbX6] octahedra, which share corners and faces, and contain intercalated DMA cations. Very interestingly, they display dielectric transitions, which are related to a partial order–disorder process of the DMA cations between 160 and 260 K. Additionally, these new layered hybrids exhibit a broadband photoluminiscent emission, which is related to the structural distortions of the [PbX6] octahedra. These findings not only open up large possibilities for future optoelectronic applications of these materials, but they also offer a novel playground for an easy modulation of electrical and optical properties of hybrid organic–inorganic materials. We anticipate that this novel A7Pb4X15 formula can be adequate to tune the family of the ...

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 observ...

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.

[Abstract] In this work, we show that the hybrid material Co2(1,4-bdc)2(dabco)•[4DMF•1H2O], shows an apparent colossal dielectric constant at room temperature (r5000 at 300 K for =100 Hz). Nevertheless, such response does not imply colossal polarizability processes, as its dielectric constant is not purely intrinsic, but is greatly enhanced by the activation of extrinsic dielectric effects close to room temperature associated to the diffusion of numerous guest molecules through the channels. If such extrinsic contributions are eliminated or reduced, the values of the dielectric constant turn to be much smaller, as observed in the closely related Co2(1,4-bdc-NH2)2(dabco)•[7/2DMF•1H2O], Co2(1,4-ndc)2(dabco) •[3DMF•2H2O] and Ni2(1,4-bdc)2(dabco)•[3DMF•1/2H2O] compounds. Therefore, we warn about the imperious necessity of distinguishing between intrinsic and extrinsic effects in electrically inhomogenous MOF materials that display a certain conductivity in order to adequately interpret their dielectric behavior Ministerio de Economía y Competitividad; MAT2010-21342-C02-01 Xunta de Galicia; PGIDIT10PXB103272PR

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.

We introduce the magnetotransport properties of Gd 1-x Sr x CoO 3 (0 < x ≤ 0.30) materials. These compounds are semiconducting and show a magnetic transition at T c 160 K associated with the onset of magnetic order of cobalt ions within superparamagnetic clusters, which have a freezing point T B < T c . Very remarkably, the more resistive samples showed rather large magnetoresistance at the lowest available temperature: MR max (x = 0.10) -16% at T = 4.2 K under H max = 40 kOe. We relate these results to the inhomogeneous electronic structure of these cobaltates and to the presence of the paramagnetic Gd 3+ sublattice, which at low temperatures influences the cobalt ions of the superparamagnetic clusters, provoking an increase in the size of the hole-rich regions and in the hopping probability of the charge carriers, and gives rise to the negative magnetoresistance observed.