Slow Magnetic Relaxation of a 12-Metallacrown-4 Complex with a Manganese(III)-Copper(II) Heterometallic Ring Motif.

The heterobimetallic metallacrown (MC), (TMA)2{Mn(OAc)2[12-MCMn(III)Cu(II)N(shi)-4](CH3OH)}·2.90CH3OH, 1, where TMA+ is tetramethylammonium, -OAc is acetate, and shi3- is salicylhydroximate, consists of a MnII ion captured in the central cavity and alternating unambiguous and ordered manganese(III) and copper(II) sites about the MC ring, a first for the archetypal MC structure design. DC-magnetometry characterization and subsequent simulation with the Spin Hamiltonian H = -J1(s1 + s3)·s5 - J2(s2 + s4)·s5 - J3Σi=14si·si+1 + d(sz,12 + sz,32) + µBΣj=15gjsj·B indicates an S = 5/2 ground state and a sizable axial zero-field splitting on MnIII. AC-susceptibility measurements reveal that 1 displays slow magnetization relaxation akin to single-molecule magnet (SMM) behavior.

Poling-Written Ferroelectricity in Bulk Multiferroic Double-Perovskite BiFe0.5Mn0.5O3.

We present a comprehensive study of the electrical properties of bulk polycrystalline BiFe0.5Mn0.5O3, a double perovskite synthesized in high-pressure and high-temperature conditions. BiFe0.5Mn0.5O3 shows an antiferromagnetic character with TN = 288 K overlapped with an intrinsic antiferroelectricity due to the Bi(3+) stereochemical effect. Beyond this, the observation of a semiconductor-insulator transition at TP ≈ 140 K allows one to define three distinct temperature ranges with completely different electrical properties. For T > TN, electric transport follows an ordinary thermally activated Arrhenius behavior; the system behaves as a paramagnetic semiconductor. At intermediate temperatures (TP < T < TN), electric transport is best described by Mott's variable range hopping model with lowered dimensionality D = 1, stabilized by the magnetic ordering process and driven by the inhomogeneity of the sample on the B site of the perovskite. Finally, for T < TP, the material becomes a dielectric insulator, showing very unusual poling-induced soft ferroelectricity with high saturation polarization, similar to the parent compound BiFeO3. Under external electric poling, the system irreversibly evolves from antiferroelectric to polar arrangement.

Improper Ferroelectric Contributions in the Double Perovskite Pb2Mn0.6Co0.4WO6 System with a Collinear Magnetic Structure.

The physical characterization and the extended crystallographic study of the double perovskite system Pb2Mn0.6Co0.4WO6 indicate an improper ferroelectric contribution to the polarization induced by the magnetic ordering. In the paramagnetic phase, the compound displays a centrosymmetric orthorhombic double perovskite structure with the Pmcn1' symmetry. The structure is strongly distorted by the lead stereoactivity. Magnetization measurements show two magnetic transitions at 188 and 9 K, but the time-of-flight neutron diffraction data provide evidence for a long-range magnetic ordering only below the second transition. Quantitative structure refinements combined with a comprehensive symmetry analysis indicate the Pm'c21' magnetic space group to be the adequate symmetry to describe the structural distortions and spin ordering in the ground state of the system. The symmetry implies a coexistence of a spontaneous ferromagnetic moment and a ferroelectric polarization along the orthogonal b- and c-axes, respectively, in the long-range ordered structure. Macroscopic measurements confirm the presence of the spontaneous polarization also below the first transition at 188 K, where only short-range magnetic correlations are evidenced by diffuse scattering in neutron diffraction.

Structural and electric evidence of ferrielectric state in Pb2MnWO6 double perovskite system.

In this paper we describe the new ferri-electric compound Pb2MnWO6 (PMW), a double perovskite that can be considered as a novel structural prototype showing complex nuclear structure and interesting electric properties. According to single-crystal synchrotron data, PMW crystallizes in the noncentrosymmetric polar group Pmc21, in which the two symmetry-independent lead atoms give rise to a ferrielectric arrangement. The accurate crystallographic characterization indicates the presence of a complex distortion of the perovskite lattice driven by the local instability induced by the 6s(2) lone pair of the lead atoms. These peculiar structural features are confirmed by the complete electrical characterization of the system. Dielectric and transport measurements indicate an insulating character of the sample, while pyroelectric measurements point out a ferrielectric state characterized by different contributions. The magnetic transition at 45 K is accompanied by a magnetostrictive effect indicating a probable spin-lattice coupling. The characterizations carried out on PMW, showing the evidence of a coexistence of antiferromagnetism and ferrielectricity at low temperature, could lead to the definition of a new class of multiferroic materials.

Triangular exchange interaction patterns in K3Fe6F19: an iron potassium fluoride with a complex tungsten bronze related structure.

The synthesis and structural and magnetic characterizations of K3Fe6F19, a new iron potassium fluoride with a complex tungsten bronze related structure, are presented. This phase was found during the investigation of relatively low-temperature (600 °C) synthesis conditions of classical tetragonal tungsten bronze (TTB) fluorides and can be considered an intermediate that forms at this temperature owing to faster crystallization kinetics. The K3Fe6F19 compound has an orthorhombic structure (space group Cmcm (63), a = 7.6975(3) Å, b = 18.2843(7) Å, c = 22.0603(9) Å) related to the TTB one, where the perovskite cage is substituted by a large S-shaped channel simultaneously occupied by two potassium atoms. The magnetic structure, characterized by magnetization measurements on an oriented single crystal and powder neutron diffraction, is dominated by the presence of interconnected double stripes of antiferromagnetic triangular exchange interaction patterns alternately rotated in clock- and anticlockwise fashion. The magnetic order takes place in a wide temperature range, by increasing progressively the interaction dimensionality.

Magnetic particle monitoring on leaves in winter: a pilot study on a highly polluted location in the Po plain (Northern Italy).

Environmental monitoring in Northern Italy, one of the most polluted areas in Europe, is of paramount importance. Leaf monitoring throughout magnetic and scanning electron microscopy (SEM-EDS) analysis could be considered a good complementary analysis to sampling stations, but the lack of evergreen plants in the northern Italy towns may hinder magnetic leaf analysis in the winter season. Therefore, we tested three species of urban vegetation, which are evergreen and commonly found in urban environment, namely Hedera helix L., Parietaria officinalis L. and Rubus caesius L. Magnetic susceptibility, chosen as a simple parameter suitable for monitoring, was measured in seven stations, during the period 25 January 2019 to 8 March 2019 at a weekly step, in the cities of Torino and Parma in the same days. P. officinalis and R. caesius showed the best response, but also H. helix was suitable to detect highly polluted areas. In Torino, the magnetic susceptibility decreased in the last sampling, together with PM10, whereas in Parma it increased, likely for the beginning of the academic period in the University Campus. SEM-EDS analysis was done comparing leaves from the same plant sampled in February 2019, in highly polluted conditions, and in May 2020, after 2 months of very limited traffic, due to national lockdown. Silicate grains of natural minerals, sized between 10 and 20 µm, are present in both samples, whereas Fe oxides, about one micron size, possibly coming from car brake consumption, are prominent in the February 2019 sample. Magnetic susceptibility of leaves form the examined species looks promising to spot urban sites with high metal pollution.

γ-BaFe2O4: a fresh playground for room temperature multiferroicity.

Multiferroics, showing the coexistence of two or more ferroic orderings at room temperature, could harness a revolution in multifunctional devices. However, most of the multiferroic compounds known to date are not magnetically and electrically ordered at ambient conditions, so the discovery of new materials is pivotal to allow the development of the field. In this work, we show that BaFe2O4 is a previously unrecognized room temperature multiferroic. X-ray and neutron diffraction allowed to reveal the polar crystal structure of the compound as well as its antiferromagnetic behavior, confirmed by bulk magnetometry characterizations. Piezo force microscopy and electrical measurements show the polarization to be switchable by the application of an external field, while symmetry analysis and calculations based on density functional theory reveal the improper nature of the ferroelectric component. Considering the present findings, we propose BaFe2O4 as a Bi- and Pb-free model for the search of new advanced multiferroic materials.

Magnetic and SEM-EDS analyses of Tilia cordata leaves and PM10 filters as a complementary source of information on polluted air: Results from the city of Parma (Northern Italy).

In this work, both PM10 filters and leaves have been collected, on a daily basis, over a period of five months and compared systematically. Filters were taken from an air-quality monitoring station and leaves from two Tilia cordata trees, both located near the railway station of Parma. SEM-EDS analysis on the surface and across the leaves shows that magnetic particles are almost entirely made of magnetite, and that they are found invariably on the leaves surface. The saturation isothermal magnetic remanence (SIRM) shows that for both filters and leaves the magnetic fraction mainly consists of a low coercivity, magnetite-like phase. The magnetic signals of filter and leaves and atmospheric PM concentrations are compared. The correlation is better for filters, mostly with parameters related to vehicular pollution, and improved for both filters and leaves once data were averaged on a 10 days basis. Filters and leaves equally show an increase in magnetic signal during the fall-winter period together with PM10 content. The comparison between leaves and filters shows that: 1) leaves give a qualitative picture, and in our case they could be used as environmental proxies after averaging the results over multiple days; 2) the correlation with PM10 is weaker, indicating that there is a PM10 contribution from non-magnetic particles, like calcite and clay minerals, pollen and spores; 3) multidomain particles contribution from filters indicates a strong relation with vehicular polluters, suggesting the important role of larger particles; 4) magnetization from leaves and filters are weakly related, due to the different sampling lapse.

Giant magneto-electric coupling in 100 nm thick Co capped by ZnO nanorods.

Here we report a giant, completely reversible magneto-electric coupling of 100 nm polycrystalline Co layer in contact with ZnO nanorods. When the sample is under an applied bias of ±2 V, the Co magnetic coercivity is reduced by a factor 5 from the un-poled case, with additionally a reduction of total magnetic moment in Co. Taking into account the chemical properties of ZnO nanorods measured by X-rays absorption near edge spectroscopy under bias, we conclude that these macroscopic effects on the magnetic response of the Co layer are due to the microstructure and the strong strain-driven magneto-electric coupling induced by the ZnO nanorods, whose nanostructuration maximizes the piezoelectric response under bias.

A comprehensive study of the magnetic properties of the pyroxenes series CaMgSi2O6-Co2Si2O6 as a function of Co content.

We report a detailed study on the magnetic properties of the pyroxene series M2M1Si2O6, with M2 = Ca and M1 = Mg, where magnesium and then calcium are progressively substituted by cobalt. For cobalt site occupancy larger than 0.7 at the M1 site, a collinear antiferromagnetic phase is detected for T < T N1 = 12 K with a monodimensional character (i.e. M1 site intra-chain order parallel to c axis). Moreover the magnetization easy axis has been estimated to lie roughly along the [1 0 1] direction. Cobalt content ⩾0.5 at the M2 site (overall content 1.5) determines the formation of a new independent antiferromagnetic order with higher Néel temperature, involving only the M2 site intra-chain interactions. The incoming M2 site order is accompanied by a lowering of the space symmetry which yields to a weakly ferromagnetic resultant due to spin canted distribution of the magnetic moments either along the M1 or M2 chains. Furthermore, metamagnetic transitions are observed for both M1 and M2 site intra-chain orders at relatively low critical magnetic fields, around 2 T, suggesting that this series of pyroxenes can be used as a model system for investigating the fundamental aspects of magnetism in the matter.

Large Magnetization and Reversible Magnetocaloric Effect at the Second-Order Magnetic Transition in Heusler Materials.

In contrast to rare-earth-based materials, cheaper and more environmentally friendly candidates for cooling applications are found within the family of Ni-Mn Heusler alloys. Initial interest in these materials is focused on the first-order magnetostructural transitions. However, large hysteresis makes a magnetocaloric cycle irreversible. Alternatively, here it is shown how the Heusler family can be used to optimize reversible second-order magnetic phase transitions for magnetocaloric applications.

Field effects on spontaneous magnetization reversal of bulk BiFe0.5Mn0.5O3, an effective strategy for the study of magnetic disordered systems.

We report a comprehensive study of the spontaneous magnetization reversal (MRV) performed on the disordered polycrystalline perovskite BiFe(0.5)Mn(0.5)O(3), an intriguing compound synthesized in high pressure-high temperature conditions. In disordered systems, the origin of MRV is not completely clarified, yet. In BiFe(0.5)Mn(0.5)O(3), compositional disorder involves the ions on the B-site of the perovskite determining the presence of mesoscopic clusters, characterized by high concentrations of iron or manganese and thus by different resultant magnetization. This leads to the observation of two singular fields H(1) and H(2) dependent on the degree of inhomogeneity, unpredictably changing from sample to sample due to synthesis effects. These fields separate different magnetic responses of the system; for applied fields H < H(1), the Fe and Mn clusters weakly interact in a competitive way, giving rise to MRV, while for an intermediate field regime the energy of this weak interaction becomes comparable to the energy of the system under field application. As a consequence, the zero field cooled magnetization thermal evolution depends on the sample degree of inhomogeneity. In this field regime, applied field Mössbauer spectroscopy indicates that the iron rich clusters are highly polarized by the field, while the largest part of the material, consisting of AFM clusters characterized by axial anisotropy and uncompensated moments, shows soft or hard magnetism depending on T. Above the higher singular field, the M(T) curves show the trend expected for a classical antiferromagnetic material and the competitive character is suppressed. The MRV phenomenon results to be highly sensitive on both the thermal and magnetic measurement conditions; for this reason the present work proposes a characterization strategy that in principle has a large applicability in the study of disordered perovskites showing similar phenomenology.