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[Abstract] In this work we focus in setting the limits of the tolerance factor and the size of the A-cations that stabilize the perovskite structure in hybrid dicyanamide compounds [A][Mn(dca)3]. For this purpose, we propose an alternative, simple approach to calculate a more realistic effective ionic radius for the large and anisotropic A-cations often present in these type of compounds. We test the proposed procedure by analysing the crystal structures of [A][Mn(dca)3] dicyanamide hybrids reported in the literature and recalculating the tolerance factors of such compounds, as well as by preparing five new [A][Mn(dca)3] members, discussing also the influence of the A-cation shape in the stability limits of the perovskite structure. Interestingly, such methodology is not only useful to develop new compounds of the emerging family of (multi)functional multi(stimuli)-responsive dicyanamide materials but can also be applied to other hybrid organic-inorganic perovskites and related materials. As for financial support, the authors thank Ministerio de Economía y Competitividad MINECO and EU-FEDER (projects MAT2017-86453-R and PDC2021-121076-I00), and Xunta de Galicia for the collaboration agreement “Development of research strategic actions Universidade da Coruña I ​+ ​D ​+ ​i 2021–2022: CICA-Disrupting Projects 2021SEM-A3 (NanoCool). J.G.-B. and J.M.B.-G. acknowledge Xunta de Galicia for Predoctoral and Postdoctoral Fellowships, respectively. I.D.-F thanks Ministerio de Universidades for a FPU Predoctoral Fellowship. A. G.-F. and U.B.C thank the Carl Tryggers foundation and the Göran Gustafsson foundation for financial support

We present a temperature-dependent Raman scattering study of a [(CH

We report giant reversible barocaloric effects in [(CH3)4N]Mn[N3]3 hybrid organic–inorganic perovskite, near its first-order cubic-monoclinic structural phase transition at T0 ∼ 305 K. When driving the transition thermally at atmospheric pressure, the transition displays a large change in entropy of ∼80 J K−1 kg−1 and a small thermal hysteresis of ∼7 K, as well as a large change in volume of ∼1.5%. When driving the transition with pressure near room temperature, the transition displays large changes in entropy of ∼70 J K−1 kg−1, which represent a giant barocaloric response. Hybrid perovskites with similar barocaloric response and lower operating temperatures may find applications in environmentally friendly cooling.

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 °C (315 K) and 29 °C (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 permittivity 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 the coexistence of multifunctional properties that can be useful for both solar thermal and electric energy storage.

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG [Abstract] 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. This MOF compound exhibits colossal thermal changes of ΔS ∼ 311 J K–1 kg–1 and ΔH ∼ 93 kJ kg–1 at room temperature (298 K) and under only 16 bar, pressure which is similar to that of common gas refrigerants at the same operating temperature (for instance, p(CO2) ∼ 64 bar and p(R134a) ∼ 6 bar) and noticeably lower than p > 1000 bar of most solid barocaloric materials. Furthermore, MIL-53(Al) can operate in a very wide temperature range from 333 K down to 254 K, matching the operating requirements of most HVAC systems. Therefore, these findings offer new eco-friendly alternatives to the current refrigeration systems that can be easily adapted to existing technologies and open the door to the innovation of future cooling systems yet to be developed. This work was financially supported by Ministerio de Economía y Competitividad MINECO and EU-FEDER (projects MAT2017-86453-R and PDC2021-121076-I00), Xunta de Galicia and IACOBUS Programme. Funding for open access fee was provided by Universidade da Coruña/CISUG

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.

We have been able to prepare two new lead halides with the formula DMAPbX3 (where DMA is dimethylammonium and X is Cl− or Br−), which display a 4H-hexagonal perovskite polytype, an unusual crystal structure in hybrid organic–inorganic perovskites. Both compounds experience a first-order phase transition, the chloride at ∼320 K and the bromide at ∼250 K, which involves two cooperative processes: an off-center shift of the lead cations and an order–disorder process of the DMA cations. Additionally, a sharp dielectric transition is associated with this structural transition in both hybrids. Both compounds are semiconductors with band gap values of 3.5 eV (X: Cl−) and 3.0 eV (X: Br−). Also, the LT-phase of the Br− compound displays a broad red light photoluminescence (PL) emission (620 nm) and PLE excitation with the maximum at a soft UV wavelength (360 nm). This broadband emission and large Stokes-shifted PL seem to be related to a self-trapped exciton mechanism. Therefore, the uncommon 4H-hexagonal perovskite is a promising crystal structure for understanding and designing new hybrid materials with broad photoluminescent emission and dielectric properties.

In this work, we study the structural changes of the polar [NH4][Cd(HCOO)3] hybrid perovskite under external hydrostatic pressure. We report a reversible framework rearrangement as a function of pressure characterized by: (i) a gradual modification of one formate ligand, which changes its coordination mode from a bridging syn–anti mode at atmospheric pressure (LP-phase) to a chelating-anti mode at high-pressure (HP-phase) and (ii) a change in the coordination of the Cd2+ cations from six-coordinated (LP-phase) to hepta-coordinated (HP-phase). Very interestingly, this unprecedented framework arrangement displays a large electrical polarization. For instance, the polarization value observed at p = 17.7 GPa is about four times the polarization at atmospheric pressure. Therefore, we report that the external pressure induces a novel framework rearrangement in the polar [NH4][Cd(HCOO)3] hybrid perovskite with enhanced electrical polarization. This structure–property relationship offers new insights for designing novel ferroelectric materials based on pressure-responsive hybrid perovskite materials.

A systematic study of the thermal decomposition of hybrid perovskites of formula [AH][M(HCOO)3] under inert atmosphere was performed by means of thermogravimetry and simultaneous infrared spectroscopy of the evolved gases. The influence of: (i) the metal ion of the [M(HCOO)3]- framework and (ii) the guest [AH]+ cation, in the composition of the final residue was evaluated. In this work, it has been demonstrated that these materials can be used as precursors of metal or metal-oxide compounds—obtained free of carbon—, and that the composition of the final residue is determined by the standard reduction potential of the metal cation of the framework.

In Solid-State Chemistry, a well-known route to obtain new compounds and modulate their properties is the formation of solid solutions, a strategy widely exploited in the case of classical inorganic perovskites but relatively unexplored among emergent hybrid organic–inorganic perovskites (HOIPs). In this work, to the best of our knowledge, we present the first dicyanamide-perovskite solid solution of [TPrA][Co0.5Ni0.5(dca)3] and study its thermal, dielectric and optical properties, comparing them with those of the parent undoped compounds [TPrA][Co(dca)3] and [TPrA][Ni(dca)3]. In addition, we show that the prepared doped compound can be used as a precursor that, by calcination, allows CNTs with embedded magnetic Ni:Co alloy nanoparticles to be obtained through a fast and much simpler synthetic route than other complex CVD or arc-discharge methods used to obtain this type of material.

Temperature-dependent Raman scattering and differential scanning calorimetry were applied to the study of the hybrid organic-inorganic azide-perovskite [(CH3)4N][Cd(N3)3], 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&middot, kg&minus, 1 K&minus, 1, together with both a positive high barocaloric (BC) coefficient |&delta, Tt/&delta, P| ~ 12.39 K kbar&minus, 1 and an inverse barocaloric (BC) coefficient |&delta, P| ~ &minus, 6.52 kbar&minus, 1, features that render this compound interesting for barocaloric applications. As for the obtained Raman spectra, they revealed that molecular vibrations associated to the NC4, N3&ndash, and CH3 molecular groups exhibit clear anomalies during the phase transitions, which include splits and discontinuity in the phonon wavenumber and lifetime. Furthermore, variation of the TMA+ and N3&ndash, modes with temperature revealed that while some modes follow the conventional red shift upon heating, others exhibit an unconventional blue shift, a result which was related to the weakening of the intermolecular interactions between the TMA (tetramethylammonium) cations and the azide ligands and the concomitant strengthening of the intramolecular bondings. Therefore, these studies show that Raman spectroscopy is a powerful tool to gain information about phase transitions, structures and intermolecular interactions between the A-cation and the framework, even in complex hybrid organic-inorganic perovskites with highly disordered phases.

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 ...

Cs23Mn16O23 was synthesized via the azide/nitrate route from mixtures of Mn2O3, CsNO3, and CsN3. This manganese(II/III) mixed-valent oxide, which contains only one Mn3+ besides 15 Mn2+ cations, was studied by single-crystal X-ray diffraction and magnetic susceptibility measurements. Its crystal structure [P1, Z = 1, a = 1114.26(2), b = 1185.53(2), c = 1205.39(2) pm, α = 70.596(1), β = 80.377(2), γ = 83.072(2)°, R1 = 0.033] is based on a honeycomb-like arrangement of cesium atoms, providing the space for two different types of one-dimensional polyoxomanganate anions, illustrated by the syntax Cs23[MnO2]4[Mn3O5]4. Magnetic susceptibility measurements indicate dominant antiferromagnetic intra-chain interactions present already at ambient temperature and long range inter-chain magnetic ordering at 11 K.

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., Designing mechanically and chemically robust liquid-repellent surfaces remains a long-standing challenge. Here, Wang and colleagues report a microfluidic emulsion templating strategy to fabricate bioinspired omniphobic porous membranes with remarkable durability.

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...

Spin-phonon coupling in rare-earth based manganites with double perovskite structure plays a crucial role in the magnetoelectric properties of these ferromagnetic materials. Particularly, on Y2CoMnO6 (YCMO), it is assumed that spin-phonon coupling is related to the induced ferroelectric polarization. This confers to YCMO a multiferroic characteristic. In this work, we probed the spin-phonon coupling in YCMO by temperature-dependent Raman spectroscopy measurements in ceramic samples obtained by the nitrate decomposition method. Raman scattering revealed some anomalies that could be attributed to a weak spin-phonon coupling, an unconventional behavior for rare-earth based manganites with double perovskite structure, in which the coupling does not fit with the quadratic magnetization.

In this work, the incorporation of dicyanamide building blocks in organic–inorganic hybrid compounds is found to be a promising strategy for the synthesis of multiwalled carbon nanotubes embedded with magnetic nanoparticles (M@CNTs). Following a novel one-step, scalable and fast synthetic route, M@CNTs are obtained by simple calcination of the organic–inorganic hybrid perovskite [TPrA][M(dca)3] (TPrA = tetrapropylammonium, M = Ni2+ and Co2+, dca = dicyanamide). The resulting M@CNTs (M = Ni and Co) display a regular morphology and an essentially mesoporous network of ∼250 m2 g−1, whereas the Co@CNT composite displays a broad pore size distribution (PSD) up to 6 nm, Ni@CNTs show a strictly controlled unimodal PSD, centered at around 5 nm. Monitoring of their thermal decomposition by X-ray diffraction, electron microscopy, thermogravimetric and spectroscopic analyses allows proposing a calcination mechanism and establishing the conditions to obtain optimal materials. Moreover, magnetization studies reveal a ferromagnetic behaviour of the obtained M@CNTs, with small coercive fields due to the size of the magnetic nanoparticles. In addition, preliminary assays of oil adsorption–desorption capacity reveal a promising potential for spilled oil recovery using this easily-synthesized materials. All these physicochemical properties make these composites good candidates for other nitrogen-rich CNT common applications., The authors are grateful for the financial support from Ministerio de Economía y Competitividad MINECO and EU‐FEDER under project ENE2014‐56237‐C4‐4‐R and Xunta de Galicia under project GRC2014/042. J. M. B.‐G. wants to thanks Barrié Foundation for a predoctoral fellowship and S. Y.‐V. to the Xunta de Galicia for a postdoctoral fellowship

By a wet-chemistry route we have been able to effectively dope the CHA2PbBr4 compound, a ferroelectric compound with photovoltaic effect, with different amounts of Mn2+ obtaining three pure compounds CHA2Pb1-xMnxBr4 with x = 0.05, 0.07 and 0.11. At room temperature the crystal structure of these new Mn-doped compounds present an orthorhombic symmetric with polar space group Cmc21, as in the case of the undoped compoud (x = 0). Very interestingly, the doped compounds exhibit a broad PL emissions at room temperature, with a maximum around 605 nm and a long PL lifetime (~0.55 ms), whose intensity increases further upon cooling. The observed PL emission is induced from an energy transfer from host semiconductor to the d-orbitals of Mn2+ cation. In addition, we have explored the capability of these materials to act as chemical sensors for volatile organic compounds and report the selective luminescence vapochromic response in this family of compounds. Therefore, the here presented Mn-doped CHA2Pb1-xMnxBr4 compounds belong to the scarce and desirable group of multifunctional materials, where not only ferroelectric and photovoltaic properties can coexist but also photoluminescence and vapochromic properties, rendering them extremely interesting for a large number of potential practical applications.

In this work we prepare and study the M(dca) 2 pyz compounds, where dca = polar dicyanamide N(CN) 2 − ligand, pyz = pyrazine (C 4 H 4 N 2 ) ligand and M = Fe 2+ , Co 2+ and Zn 2+ that, according to DSC display a first order phase transition, at T t ∼ 270 K (Fe), ∼250 K (Co) and ∼240 K (Zn). Very interestingly these compounds, which consist of a rather robust framework with incorporated polar dca ligands, and which does not host guest species in the cavities of the structure, display a dielectric anomaly associated to such phase transition. This latter in fact corresponds to the structural transition from the disordered HT-phase (space group Pnma ) to the ordered LT-phase (space group P 2 1 / n ). From a detailed analysis of the dipole distributions in each of these crystal structures we conclude that the polar dca ligands, which bridge two transition metal cations, display a cooperative electrical arrangement, in which the dipoles of each of the two interpenetrated networks show a ferroelectric (FE) arrangement; nevertheless, the relative antiparallel orientation of both networks finally results in net antiferroelectric (AFE) arrangements both in the LT- and HT-polymorphs. Very interestingly, the dynamic disorder of the dca ligands at T t gives rise to the observed dielectric anomaly. These materials constitute, therefore, an example of hybrid organic–inorganic compounds where the dielectric response directly arises from the framework –and not from polar guest species– which is a very interesting and novel approach in the search for materials in which the dielectric and magnetic properties can couple more strongly.

In this work, we have successfully synthesized hollow microtubular crystals of the metal–organic framework (MOF) [Co2(NH2-bdc)2(dabco)]·[G] {G = H2O, N,N-dimethylformamide (DMF); NH2-bdc =2-amino-1,4-benzenedicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane} by a very simple coordination-modulation method that avoids the use of an external modulator. Additionally, we have obtained the corresponding hollow microtubular crystals of Co3O4 through the solid-state thermolysis of the Co-MOF material at 400 °C. The as-prepared Co3O4 crystals exhibit the typical magnetic behavior for a nanostructured material with good crystallinity. Thus, this coordination-modulation method provides a simple route for the preparation of nanostructured porous frameworks and derived oxides and opens a way to prepare new materials with advanced properties.

The perovskite azido compound [(CH3)4N][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)4N]+ 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)4N][Mn(N3)3] is a singular material in which three ferroic orders coexist even above room temperature. Triple-ferroic hybrid perovskite: The azido perovskite compound [(CH3)4N][Mn(N3)3] is a singular multiferroic material in which the three ferroic orders (electric, elastic, and magnetic) coexist even above room temperature (see figure).

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., The authors are grateful for the financial support from Ministerio de Economía y Competitividad MINECO (MINECO) ENE2014-56237-C4-4-R and Xunta de Galicia under the project GRC2014/042. J. M. B.-G. also wants to thank Barrié Foundation for a predoctoral fellowship and S. Y.-V. to the Xunta de Galicia for a postdoctoral grant (Plan I2C).

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, er′ ∼ 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 (c) the potential of these materials for molecular transport applications.

We report the barocaloric performance of cadmium-dicyanamide perovskite [(CH3CH2CH2)4N]Cd[N(CN)2]3 ([TPrA]Cd[dca]3). The introduction of Cd, a large second-row post-transition metal, into this hybrid organic–inorganic perovskite structure leads to three separate thermally driven phase transitions and four polymorphs, which we characterize in full using temperature-dependent X-ray diffraction and temperature-dependent calorimetry. Amongst these transitions, the non-isochoric orthorhombic to tetragonal phase transition at high temperatures, with a large volume change of ∼0.4%, leads to a large reversible pressure-driven isothermal change in entropy of ∼11.5 J K−1 kg−1, and a giant barocaloric tunability of the transition temperature with pressure of ∼38.2 K kbar−1, which are both desirable for future low-pressure barocaloric cooling applications.

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.

We investigate the magnetic ordering and the magnetization dynamics (from kHz to THz time scales) of the double perovskite Lu2MnCoO6 using elastic neutron diffraction, muon spin relaxation, and micro-Hall magnetization measurements. This compound is known to be a type II multiferroic with the interesting feature that a ferromagneticlike magnetization hysteresis loop couples to an equally hysteretic electric polarization in the bulk of the material despite a zero-field magnetic ordering of the type ↑↑↓↓ along Co-Mn spin chains. Here we explore the unusual dynamics of this compound and find extremely strong fluctuations, consistent with the axial next-nearest-neighbor Ising (ANNNI) model for frustrated spin chains. We identify three temperature scales in Lu2MnCoO6 corresponding to the onset of highly fluctuating long-range order below TN = 50 ± 3 K identified from neutron scattering, the onset of magnetic and electric hysteresis, with change in kHz magnetic and electric dynamics below a 30 K temperature scale, and partial freezing of ∼MHz spin fluctuations in the muon spin relaxation data below 12 ± 3 K. Our results provide a framework for understanding the multiferroic behavior of this compound and its hysteresis and dynamics.

Here we present an in-depth study of the magnetic properties of a family of metal–organic perovskites ABX3, [CH3NH3][M(HCOO)3] in which A = CH3NH3+ is the methylammonium cation, B = M is a divalent metal cation (Mn2+, Co2+, Ni2+ or Cu2+), and X is the formate anion (HCOO−). The magnetic properties have been measured on powdered samples and along the different orientations of mm-sized single crystals. They display spin-canted weak ferromagnetism with Néel temperatures of 8.0 K (Mn2+), 15.7 K (Co2+) and 34 K (Ni2+), which are inversely proportional to the ionic radii of the metal cations. The Cu2+ member displays low-dimensional magnetism as a result of orbital ordering of the Cu2+ d orbitals originating from a Jahn–Teller distortion. Pulsed-field magnetization experiments (fields of up to 60 T at temperatures down to 0.6 K) show that Mn2+, Co2+ and Ni2+ formates display cation-characteristic spin flop transitions. A saturation magnetization value of 5 μB (at 12.5 T) was observed for Mn2+, meanwhile the Co2+ formate shows an orientation dependent quasi saturation (5.1 μB at 21 T along [101] vs. 5.8 μB at 26 T along [010]). The different isotropic/anisotropic behaviour can be explained by the orbital contribution to the magnetic response The Spanish authors are grateful for financial support from Ministerio de Economía y Competitividad (MINECO) (Spain) and EU under the project ENE2014-56237-C4-4-R, and Xunta de Galicia under the project GRC2014/042. L. C. G.-A. acknowledges UDC for a predoctoral fellowship and Fundación Barrié for the research stay grant at LANL. Work at LANL, A. P. H. and B. P.-D.'s visit to LANL were funded by the Laboratory Directed Research and Development program at LANL. The NHMFL pulsed-field facility is funded by the U.S. National Science Foundation through Cooperative Grant No. DMR-1157490, the State of Florida, and the U.S. Department of Energy SI

[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

In this work, we present the new compounds Pr 0.50 Ln 0.50 BaCo 2 O 5+ δ (Ln: Pr, Nd, Sm, Eu, Gd, Tb and Dy) that we have synthesized as pure phase polycrystalline materials by the Pechini method. Doping the A site with a second heavier lanthanide promotes smaller oxygen stoichiometry, providing an alternative way to modify the oxygen content of these Pr-cobalt oxides by means of changing the PrLn ratio. According to powder X-Ray diffraction the compounds display an average tetragonal structure. The presence of smaller Ln ions together with a smaller amount of oxygen gives rise to higher Seebeck coefficients, specially from PrEu to PrDy, and to a substantial increase of the resistivity below 200 K. As a result the highest power factor is displayed by the Pr 0.50 Eu 0.50 BaCo 2 O 5.69 sample at ∼125 K, PF max ∼0.154 μW K −2 cm −1 , value that is two orders of magnitude higher than that shown by the starting PrBaCo 2 O 5.76 sample at the same temperature.

In this work, we focus on the influence of the oxygen content and the preparation method on the power factor of different PrBaCo2O 5+δ samples (0.54 ≤ δ ≤ 0.84). The samples have been initially synthesized by the Pechini method. Their oxygen content has been subsequently modified by annealing under argon/oxygen flow or by electrochemical oxidation/reduction. The oxygen stoichiometry has a high impact on the electrical conductivity and Seebeck coefficient of the resulting materials. Moreover, by adequately reducing their oxygen content while increasing their intergrain conductivity (by increasing the particle size and degree of sintering) the power factor of these samples can be drastically improved. The best result is shown by the PrBaCo2O5.54 sample, that was annealed at high temperature under argon flow, whose power factor is as high as 6.5 μW/K2 cm-1 at ∼135 K, more than two orders of magnitude higher than that shown by the initial PrBaCo2O 5.76 reference sample. © 2011 Elsevier B.V.

We are reporting on the dielectric properties of NaCu3(Ti3Nb)O12 and Na(Cu2.5Ti0.5)Ti4O12 which are related to the perovskite CaCu3Ti4O12 compound. The NaCu3(Ti3Nb)O12 perovskite, that is doped with Nb cations at the Ti B-site, shows high values of dielectric constant. Using impedance spectroscopy (IS), we have observed that this compound is electrically inhomogeneous, showing a semiconductive bulk and insulating grain boundaries. The presence of a semiconductive bulk seems to indicate that a charge delocalization process is taking place through the Cu A′-site. In the case of the Na(Cu2.5Ti0.5)Ti4O12 perovskite, the dielectric response comes from the bulk material and the IS results show an intrinsic homogeneous material. In this compound, the large doping of Ti cations at the Cu A′-site prevents a charge delocalization process and the material becomes insulating. These results highlight the importance of the A′-sites in the charge delocalization process. In addition, Na(Cu2.5Ti0.5)Ti4O12 provides evidence of a soft-mode behavior that could be responsible for the relatively high intrinsic dielectric constant of CaCu3Ti4O12 and related compounds. © 2009 Elsevier B.V. All rights reserved.

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.

This is the accepted manuscript of the following article: Sánchez-Andújar, M., Yáñez-Vilar, S., Biskup, N., Castro-García, S., Mira, J., Rivas, J., & Señarís-Rodríguez, M. (2009). Magnetoelectric behavior in the complex CaMn7O12 perovskite. Journal Of Magnetism And Magnetic Materials, 321(11), 1739-1742. doi: 10.1016/j.jmmm.2009.02.018 We report a magnetoelectric effect in the double perovskite CaMn7O12, that shows a complex magnetic behavior below 90 K with two magnetic phases coexisting (one ferrimagnetic and the other modulated). A second magnetic transition, associated with changes in the magnetic modulation and magnetic ordering coherence lengths of the two magnetic phases occurs at 50 K (TN2). A detailed structural characterization of this compound, that we have carried out by means of high-resolution X-ray powder diffraction, reveals an anisotropic thermal expansion of its lattice parameters at 50 K (TN2). In addition, our study of the complex permittivity of this sample as a function of temperature, frequency and magnetic field shows very interesting results below 90 K and specially below 50 K: the dielectric constant ε′r that was decreasing continuously on cooling experiences an upturn, and even more, on application of a magnetic field it shows a moderate magnetoelectric response. We attribute such dielectric behavior to the formation of electric dipoles by magnetostriction in this charge and spin ordered system, that are sensible to the presence of an external magnetic field The authors are grateful from financial support for MEC (Spain) under project FEDER MAT 2007-66696 and Xunta de Galicia under project PGIDIT06PXB103298PR. S. Yáñez-Vilar want to thank to MEC of Spain for her FPI fellowship and M. Sánchez-Andújar acknowledges to Xunta de Galicia for support under program Parga Pondal SI

Se han conseguido preparar monocristales de 10 oxidos mixtos de la serie LnMn2O5 (Ln= Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho y Er) mediante sintesis hidrotermal optimizada, en un unico paso y sin tratamientos termicos posteriores partiendo de las correspondientes sales metalicas en disolucion acuosa a 240 oC. Los monocristales obtenidos son relativamente grandes, de varias micras y su morfologia varia a lo largo de la serie: es poligonal en el caso de los compuestos de los lantanidos del inicio de la serie (Ln= Pr, Nd, Sm, Eu y Gd) y acicular en el caso de los compuestos de Y y de los lantanidos del final de la serie (Ln= Tb, Dy, Ho y Er). Tras el analisis de los productos obtenidos empleando distintas condiciones de sintesis atribuimos la diferente morfologia a una mayor velocidad de crecimiento cristalino a lo largo del eje c cuando intervienen los iones mas pequenos (Y, Tb, Dy, Ho y Er) debido a la mejor adaptacion de estos ultimos a la estructura cristalina del compuesto.

We report the magneto-transport properties of the layered mixed oxides Nd1−xSr1+xCoO4 (0 ≤ x ≤ 0.3) compounds. These materials are found to evolve towards an anomalous “cluster-glass” like behavior as x increases. The onset of the ferromagnetic order in the bidimensional phase is seen to occur in the x = 0.30 sample at Tc(2D) ≈ 125 K, followed by a blocking process around TB (2D) ≈ 55 K. In addition, present in the magnetic response of these materials is the paramagnetic contribution coming from the Nd3+ ions μ eff-N d 3+ = 3.62 μ B together with the signal coming from a minority perovskite phase, that is nevertheless not detected by powder X-ray diffraction. From the electrical point of view these materials are semiconducting and their resistivitiy decreases upon doping. In addition, at low temperatures T

In this work we introduce the use of a combined Rietveld refinement and Maximum Entropy Method (MEM), as a helpful new tool to gain insight into the charge ordering pattern present in CO-transition metal compounds. In particular we show the study made on two CO oxyborates A2OBO3 (A = Mn and Fe): (a) the Mn-oxyborate, that exhibits a strong charge lattice coupling, and whose charge ordering pattern had been previously satisfactory established from BVS analysis of single crystal X-ray diffraction data and that we have used as a test to confirm the validity of the new method; (b) the weakly charge-lattice coupled Fe-oxyborate, a compound not suitable for the BVS approach and for which nevertheless this method gives evidence for a new charge ordering pattern.

The La0.85Sr0.15CoO3 compound has been synthesized under different annealing temperatures. It has been observed that the transport properties and magnetoresistance of this compound depend on such temperatures. This response is discussed in the framework of a model of electronic phase segregation.

In this work we have measured the complex dielectric permittivity of a polycrystalline material using samples of different thickness (frequency range 20–1 MHz). The results reveal that the CaMn 7 O 12 material is electrically heterogeneous as it consists of regions of different conductivities. In this kind of electrically heterogeneous materials the variation of the dielectric permittivity as a function of temperature can be fitted to a Maxwell–Wagner model. In the case of the CaMn 7 O 12 sample this model fits only partially the experimental data and we need to include three regions of different conductivities to explain the obtained dielectric response.

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.

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., The authors are grateful for the financial support from Ministerio de Economia y Competitividad MINECO (MINECO) ENE2014-56237-C4-4-R and Xunta de Galicia under the project GRC2014/042. J. M. B.-G. also wants to thank Barrié Foundation for a predoctoral fellowship and S. Y.-V. to the Xunta de Galicia for a postdoctoral grant (Plan I2C).

After half a century of intensive and extensive studies on ferrocene [Fe(C5H5)2] and ammonia-borane (H3N·BH3), it is very exciting to observe that these “classical” compounds still hide interesting properties never described before. Despite it being well-known that they both experience phase transitions as a function of temperature, here, for the first time, we give experimental evidence for the dielectric transitions they experience associated to the former, results that we support with DFT calculations. In that context, we report that ferrocene displays a temperature-induced paraelectric to antiferroelectric transition associated with the monoclinic–triclinic transition, which implies order–disorder of the cyclopentadienyl (Cp) ligands and displacement of the Fe atoms within the ferrocene molecules. As for the ammonia-borane, we report a sharp dielectric transition at T ≈ 232 K, associated with a structural transition that combines ordering and atomic displacement of the H3N·BH3 molecules. In this case, we attribute such behaviour to the temperature dependent displacement of the H3N·BH3 molecules out-of the crystal polar c-axis The authors are grateful for financial support from Ministerio de Economía y Competitividad (MINECO) ENE2014-56237-C4-4-R and Xunta de Galicia under the project GRC2014/042. S. Y.-V. acknowledges Xunta de Galicia for a Postdoctoral fellowship SI

We present the synthesis and dielectric characterization of core–shell LaMn0.5Co0.5O3-based composites that we have prepared with the aim of improving the dielectric properties of the pure mixed oxide, especially reducing its high dielectric losses. For this purpose we have coated the LaMn0.5Co0.5O3 particles with SiO2 nanoshells ~20 nm thick. From the practical point of view, the composite material obtained shows at room temperature a still rather high dielectric constant (e'r~200 at ν = 106 Hz) while its dielectric losses are at least one order of magnitude smaller than those of the base oxide (tanδ = 0.8 at ν = 106 Hz).

We report the magnetic and transport properties of the cobalt layered mixed-oxides La1−xSr1+xCoO4 ( 0 ⩽ x ⩽ 0.40 ) . An evolution towards an anomalous “cluster-glass”-like behavior as x increases has been found. The onset of the ferromagnetic order in the layered phases occurs at around 150 K followed by a blocking process around 125 K. Also, present in the magnetic response of these materials is the signal coming from small intergrowths of a perovskite phase, also detected by TEM, although invisible for powder-X-ray diffraction. From the electrical point of view these materials are semiconducting and their resistivity decreases upon doping. Most interestingly, at low temperature these layered compounds show rather large magnetoresistance (MR). The highest effect is found in the sample with x = 0.20 that shows a magnetoresistance MR max = − 24 % at T = 15 K under a field H max = 50 kOe .

In this work, we study the dielectric properties of the layered perovskites La 3/2 Sr 1/2 NiO 4 and La 5/3 Sr 1/3 NiO 4 in the frequency range 20 Hz-1 MHz and in the temperature range 110-350 K. For this study, we have synthesized single phase polycrystalline samples by a conventional solid-state reaction. These nickelates show very high values of the dielectric constant at room temperature (e' r ∼ 10 5 ), that make them very attractive for potential applications, provided that their rather high losses can be minimized. The obtained results reveal that even if their dielectric behavior is strongly enhanced by extrinsic polarization effects, there is also a very interesting correlation between their dielectric response and their electronic state.

We present in this paper a detailed investigation of the dielectric properties of the mixed oxide CaMn7O12 that shows a charge-ordering transition at TCO = 440 K. Surprisingly, this compound presents a high dielectric constant at room temperature. Data taken at several frequencies and temperatures point to relaxor dielectric behaviour, that can be attributed to the electronic inhomogeneities present in the material. Extrinsic Maxwell–Wagner effects make a significant contribution to this dielectric response, as revealed by the studies made on samples of different particle size and using different types of contact. The intrinsic dielectric constant of this material is e �(intrinsic) ∼ 30 at room temperature, a value that is relatively high for this type of compound and that we relate to the presence of the electronic process of charge ordering in this material.

We report the dielectric response of Ca2?xPrxMnO4 (x = 0 and 0.25). Specifically, their intrinsic dielectric constants are calculated by impedance spectroscopy from the values of the obtained bulk capacitances. For Ca2MnO4, that does not show charge-order, the measured intrinsic dielectric constant is 14. The Pr doping induces charge-order in the system, and also a noteworthy increase in , that reaches a value of ~220 for x = 0.25, unusual in these kind of oxides. This result provides a new link between both phenomena.

The dielectric properties of mixed-oxide CaMn7O12 are reported. This compound exhibits a high dielectric constant at room temperature (er >1 0 4 ), for frequencies up to 10 4 Hz, values that make it very attractive for potential applications provided that its rather high losses can be minimized. Complex plane analysis of the obtained data reveal an important extrinsic contribution to these high er values; and also that the