Exploring the effect of pressure on the crystal structure and caloric properties of the molecular ionic hybrid [(CH)NOH][CoCl].

The hybrid metal halide [(CH)NOH]CoCl exhibits a first-order phase transition at ∼ 343 K. Its crystal structure and caloric properties respond significantly to moderate pressures (1-1000 bar), demonstrating potential for applications in emerging solid-state refrigeration technologies.

Empowering CO Eco-Refrigeration With Colossal Breathing-Caloric-Like Effects in MOF-508b.

Today, ≈20% of the electric consumption is devoted to refrigeration; while, ≈50% of the final energy is dedicated to heating applications. In this scenario, many cooling devices and heat-pumps are transitioning toward the use of CO as an eco-friendly refrigerant, favoring carbon circular economy. Nevertheless, CO still has some limitations, such as large operating pressures (70-150 bar) and a critical point at 31 °C, which compromises efficiency and increases technological complexity.

Order-disorder phase transition and molecular dynamics in the hybrid perovskite [(CH)NH][Mn(N)].

We present a temperature-dependent Raman scattering study of a [(CH)NH][Mn(N)] hybrid organic-inorganic azide-perovskite, in which we have analysed in detail the wavenumber and full width at half-maximum (FWHM) of lattice modes and internal modes of the NC skeleton, N and CH molecular groups. In general, the modes exhibited unusual behaviour during the phase transitions, including discontinuity in the phonon wavenumber, bandwidth, and unconventional shifts upon temperature variation. Spectral features on heating reveal the absence of significant distortions in the NC skeleton and a relatively restricted order-disorder process of the TrMA cations.

Anomalous and colossal thermal expansion, photoluminescence, and dielectric properties in lead halide-layered perovskites with cyclohexylammonium and cyclopentylammonium cations.

A detailed study of lead halide-layered perovskites with general formula APbX (where A is cyclohexylammonium (CHA) or cyclopentylammonium (CPA) cation and X is Cl or Br anion) is presented. Using variable temperature synchrotron X-ray powder diffraction, we observe that these compounds exhibit diverse crystal structures above room temperature. Very interestingly, we report some unconventional thermomechanical responses such as uniaxial negative thermal expansion and colossal positive thermal expansion in a perpendicular direction.

Discovery of Colossal Breathing-Caloric Effect under Low Applied Pressure in the Hybrid Organic-Inorganic MIL-53(Al) Material.

In this work, "breathing-caloric" effect is introduced as a new term to define very large thermal changes that arise from the combination of structural changes and gas adsorption processes occurring during breathing transitions. In regard to cooling and heating applications, this innovative caloric effect appears under very low working pressures and in a wide operating temperature range. This phenomenon, whose origin is analyzed in depth, is observed and reported here for the first time in the porous hybrid organic-inorganic MIL-53(Al) material.

Raman Spectroscopy Studies on the Barocaloric Hybrid Perovskite [(CH)N][Cd(N)].

Temperature-dependent Raman scattering and differential scanning calorimetry were applied to the study of the hybrid organic-inorganic azide-perovskite [(CH)N][Cd(N)], a compound with multiple structural phase transitions as a function of temperature. A significant entropy variation was observed associated to such phase transitions, |∆S| ~ 62.09 J·kg K, together with both a positive high barocaloric (BC) coefficient |δT/δP| ~ 12.

[(CH)NH]PbX (X = Cl and Br), 2D-Perovskite Related Hybrids with Dielectric Transitions and Broadband Photoluminiscent Emission.

We have prepared two new lead halides with the novel general formula of DMAPbX (DMA = [(CH)NH] 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 [PbX] 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.

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

In this work, we focus on [(CH)NH]PbI, a member of the [AmineH]PbI series of hybrid organic-inorganic compounds, reporting a very easy mechanosynthesis route for its preparation at room temperature. We report that this [(CH)NH]PbI compound with 2H-perovskite structure experiences a first-order transition at ≈250 K from hexagonal symmetry P6/mmc (HT phase) to monoclinic symmetry P2/c (LT phase), which involves two cooperative processes: an off-center shift of the Pb 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.

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).

Coexistence of Three Ferroic Orders in the Multiferroic Compound [(CH3 )4 N][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.

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.

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).

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.

Synthesis, crystal structure and magnetic properties of the new one-dimensional manganate Cs3Mn2O4.

Cs(3)Mn(2)O(4), a new member of the small family of ternary manganese (II/III) mixed-valent compounds, has been synthesized via the azide/nitrate route and studied using powder and single crystal X-ray diffraction, magnetic susceptibility measurements and density functional theory (DFT). Its crystal structure (P2(1)/c, Z = 8, a = 1276.33(1) pm, b = 1082.

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.