RESUMO
Photomagnetic compounds are usually achieved by assembling preorganized individual molecules into rationally designed molecular architectures via the bottom-up approach. Here we show that a magnetic response to light can also be enforced in a nonphotomagnetic compound by applying mechanical stress. The nonphotomagnetic cyano-bridged Fe(II)-Nb(IV) coordination polymer {[Fe(II)(pyrazole)4]2[Nb(IV)(CN)8]·4H2O}n (FeNb) has been subjected to high-pressure structural, magnetic and photomagnetic studies at low temperature, which revealed a wide spectrum of pressure-related functionalities including the light-induced magnetization. The multifunctionality of FeNb is compared with a simple structural and magnetic pressure response of its analog {[Mn(II)(pyrazole)4]2[Nb(IV)(CN)8]·4H2O}n (MnNb). The FeNb coordination polymer is the first pressure-induced spin-crossover photomagnet.
RESUMO
An extensive series of new LnRuO3 perovskites has been synthesized at high pressure. These ruthenium(III)-based oxides are ruthenium deficient, and high-pressure samples have compositions close to LnRu(0.9)O3. These phases stabilize ruthenium(III) which is very unusual in oxides. X-ray and neutron powder diffraction studies show that the materials adopt orthorhombic perovskite superstructures in which the RuO6 octahedra are tetragonally compressed. These distortions, and the Mott insulator properties of the materials, are driven by strong spin-orbit coupling.
RESUMO
We have performed a quantum-mechanical study of a series of stoichiometric Ni2MnSn structures focusing on pressure-induced changes in their magnetic properties. Motivated by the facts that (i) our calculations give the total magnetic moment of the defect-free stoichiometric Ni2MnSn higher than our experimental value by 12.8% and (ii) the magnetic state is predicted to be more sensitive to hydrostatic pressures than seen in our measurements, our study focused on the role of point defects, in particular Mn-Ni, Mn-Sn and Ni-Sn swaps in the stoichiometric Ni2MnSn. For most defect types we also compared states with both ferromagnetic (FM) and anti-ferromagnetic (AFM) coupling between (i) the swapped Mn atoms and (ii) those on the Mn sublattice. Our calculations show that the swapped Mn atoms can lead to magnetic moments nearly twice smaller than those in the defect-free Ni2MnSn. Further, the defect-containing states exhibit pressure-induced changes up to three times larger but also smaller than those in the defect-free Ni2MnSn. Importantly, we find both qualitative and quantitative differences in the pressure-induced changes of magnetic moments of individual atoms even for the same global magnetic state. Lastly, despite of the fact that the FM-coupled and AFM-coupled states have often very similar formation energies (the differences only amount to a few meV per atom), their structural and magnetic properties can be very different.
RESUMO
Materials that demonstrate long-range magnetic order are synonymous with information storage and the electronics industry, with the phenomenon commonly associated with metals, metal alloys or metal oxides and sulfides. A lesser known family of magnetically ordered complexes are the monometallic compounds of highly anisotropic d-block transition metals; the 'transformation' from isolated zero-dimensional molecule to ordered, spin-canted, three-dimensional lattice being the result of through-space interactions arising from the combination of large magnetic anisotropy and spin-delocalization from metal to ligand which induces important intermolecular contacts. Here we report the effect of pressure on two such mononuclear rhenium(IV) compounds that exhibit long-range magnetic order under ambient conditions via a spin canting mechanism, with Tc controlled by the strength of the intermolecular interactions. As these are determined by intermolecular distance, 'squeezing' the molecules closer together generates remarkable enhancements in ordering temperatures, with a linear dependence of Tc with pressure.