The fast growing family of organic–inorganic hybrid compounds has recently been attracting increased attention owing to the remarkable functional properties (magnetic, multiferroic, optoelectronic, photovoltaic) displayed by some of its members. Here we show that these compounds can also have great potential in the until now unexplored field of solid-state cooling by presenting giant barocaloric effects near room temperature already under easily accessible pressures in the hybrid perovskite [TPrA][Mn(dca)3] (TPrA: tetrapropylammonium, dca: dicyanamide). Moreover, we propose that this will not be an isolated example for such an extraordinary behaviour as many other organic–inorganic hybrids (metal-organic frameworks and coordination polymers) exhibit the basic ingredients to display large caloric effects which can be very sensitive to pressure and other external stimuli. These findings open up new horizons and great opportunities for both organic–inorganic hybrids and for solid-state cooling technologies.

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.

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In this work we explore the overall structural behaviour of the [(CH 3 ) 2 NH 2 ][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 proof the presence of structural phase transition at T t ~187 K (temperature at which the dielectric transition occurs) that involves a symmetry change from R-3c 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 (dT t /dP = 4.6 ± 0.1 K/kbar), so that it should be feasible to shift it to room temperature using adequate thermodynamic conditions, for instance by application of external pressure.

The hybrids [TPrA][M(dca)3] (M: Fe2+, Co2+ and Ni2+) are unique multi-sensitive materials that display multiple phase and dielectric transitions.

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.

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. 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 (E = 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 [(CH)NH]PbI is an electronic insulator and an ionic conductor, where the electronic conductivity is disfavored because of the low dimensionality of the [(CH)NH]PbI structure.

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