Pressure-Driven Metallization in Hafnium Diselenide.

The quest for new transition metal dichalcogenides (TMDs) with outstanding electronic properties operating under ambient conditions draws us to investigate the 1T-HfSe polytype under hydrostatic pressure. Diamond anvil cell (DAC) devices coupled to synchrotron X-ray, Raman, and optical (VIS-NIR) absorption experiments along with density functional theory (DFT)-based calculations prove that (i) bulk 1T-HfSe exhibits strong structural and vibrational anisotropies, being the interlayer direction especially sensitive to pressure changes, (ii) the indirect gap of 1T-HfSe tends to vanish by a -0.1 eV/GPa pressure rate, slightly faster than MoS or WS, (iii) the onset of the metallic behavior appears at ∼10 GPa, which is to date the lowest pressure among common TMDs, and finally, (iv) the electronic transition is explained by the bulk modulus - correlation, along with the pressure coefficient of the band gap, in terms of the electronic overlap between chalcogenide p-type and metal d-type orbitals.

Characterization and Decomposition of the Natural van der Waals SnSbTe under Compression.

High pressure X-ray diffraction, Raman scattering, and electrical measurements, together with theoretical calculations, which include the analysis of the topological electron density and electronic localization function, evidence the presence of an isostructural phase transition around 2 GPa, a Fermi resonance around 3.5 GPa, and a pressure-induced decomposition of SnSbTe into the high-pressure phases of its parent binary compounds (α-SbTe and SnTe) above 7 GPa. The internal polyhedral compressibility, the behavior of the Raman-active modes, the electrical behavior, and the nature of its different bonds under compression have been discussed and compared with their parent binary compounds and with related ternary materials.

Large Magnetoelectric Coupling Near Room Temperature in Synthetic Melanostibite Mn FeSbO.

Multiferroic materials exhibit two or more ferroic orders and have potential applications as multifunctional materials in the electronics industry. A coupling of ferroelectricity and ferromagnetism is hereby particularly promising. We show that the synthetic melanostibite mineral Mn FeSbO (R3‾ space group) with ilmenite-type structure exhibits cation off-centering that results in alternating modulated displacements, thus allowing antiferroelectricity to occur.

Low-Temperature Cationic Rearrangement in a Bulk Metal Oxide.

Cationic rearrangement is a compelling strategy for producing desirable physical properties by atomic-scale manipulation. However, activating ionic diffusion typically requires high temperature, and in some cases also high pressure in bulk oxide materials. Herein, we present the cationic rearrangement in bulk Mn2 FeMoO6 at unparalleled low temperatures of 150-300 (o) C.

Magnetic Interactions in the Double Perovskites R2NiMnO6 (R = Tb, Ho, Er, Tm) Investigated by Neutron Diffraction.

R2NiMnO6 (R = Tb, Ho, Er, Tm) perovskites have been prepared by soft-chemistry techniques followed by high oxygen-pressure treatments; they have been investigated by X-ray diffraction, neutron powder diffraction (NPD), and magnetic measurements. In all cases the crystal structure is defined in the monoclinic P21/n space group, with an almost complete order between Ni(2+) and Mn(4+) cations in the octahedral perovskite sublattice. The low temperature NPD data and the macroscopic magnetic measurements indicate that all the compounds are ferrimagnetic, with a net magnetic moment different from zero and a distinct alignment of Ni and Mn spins depending on the nature of the rare-earth cation.

Giant magnetoresistance in the half-metallic double-perovskite ferrimagnet Mn2FeReO6.

The first transition-metal-only double perovskite compound, Mn(2+) 2 Fe(3+) Re(5+) O6 , with 17 unpaired d electrons displays ferrimagnetic ordering up to 520 K and a giant positive magnetoresistance of up to 220 % at 5 K and 8 T. These properties result from the ferrimagnetically coupled Fe and Re sublattice and are affected by a two-to-one magnetic-structure transition of the Mn sublattice when a magnetic field is applied. Theoretical calculations indicate that the half-metallic state can be mainly attributed to the spin polarization of the Fe and Re sites.

Magnetic-structure-stabilized polarization in an above-room-temperature ferrimagnet.

Above-room-temperature polar magnets are of interest due to their practical applications in spintronics. Here we present a strategy to design high-temperature polar magnetic oxides in the corundum-derived A2BB'O6 family, exemplified by the non-centrosymmetric (R3) Ni3TeO6-type Mn(2+)2Fe(3+)Mo(5+)O6, which shows strong ferrimagnetic ordering with TC = 337 K and demonstrates structural polarization without any ions with (n-1)d(10)ns(0), d(0), or stereoactive lone-pair electrons. Density functional theory calculations confirm the experimental results and suggest that the energy of the magnetically ordered structure, based on the Ni3TeO6 prototype, is significantly lower than that of any related structure, and accounts for the spontaneous polarization (68 μC cm(-2)) and non-centrosymmetry confirmed directly by second harmonic generation.

Correlation between the crystal structure and the Curie temperature in RCu3(Mn3Fe)O12 (R = rare-earth) complex perovskites.

New members of the family of complex-perovskite oxides with the formula RCu(3)(Mn(3)Fe)O(12) (R = Ce, Pr, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) have been synthesized and characterized. Polycrystalline samples have been prepared from citrate precursors treated under moderate pressure conditions (2-3.5 GPa) and 1000 °C in the presence of KClO(4) as an oxidizing agent.

Slow magnetic relaxation in a 3D network of cobalt(II) citrate cubanes.

The synthesis, structure and magnetic properties of a 3D network based on {Co₄(cit)₄}⁸⁻ (H₄cit = citric acid) cubane units linked by octahedral Co(II) centres is reported.

Enhancement of the Curie temperature along the perovskite series RCu3Mn4O12 driven by chemical pressure of R3+ cations (R = rare earths).

The compounds of the title series have been prepared from citrate precursors under moderate pressure conditions (P = 2 GPa) and 1000 degrees C in the presence of KClO(4) as oxidizing agent. The crystal structures are cubic, space group Im3 (No. 204); the unit cell parameters linearly vary from a = 7.

Pressure-induced Jahn-Teller switching in a Mn12 nanomagnet.

Pressure-induced switching of a fast-relaxing single-molecule magnet to a slow-relaxing isomer is observed for the first time by using a combination of high pressure single-crystal X-ray diffraction and high pressure magnetic measurements.

High pressure studies of hydroxo-bridged Cu(II) dimers.

A combination of high pressure single crystal X-ray diffraction and high pressure SQUID magnetometry has been used to study three hydroxo-bridged copper(II) dimers. [Cu2(OH)2(H2O)2(tmen)2](ClO4)2 (1; tmen = tetramethylethylenediamine), [Cu2(OH)2(tben)2](ClO4)2 (2; tben = di-tbutylethylenediamine) and [Cu2(OH)2(bpy)2](BF4)2 (3; bpy = 2,2'-bipyridine) have been structurally determined to 2.5, 0.

High pressure effects on a trimetallic Mn(II/III) SMM.

A combined study of the high pressure crystallography and high pressure magnetism of the complex [Mn3(Hcht)2(bpy)4](ClO4)3.Et2O.2MeCN (1.

High pressure induced spin changes and magneto-structural correlations in hexametallic SMMs.

The first combined high pressure single-crystal X-ray diffraction and high pressure magnetism study of two polymetallic clusters is presented in an attempt to correlate the observed changes in structure with changes in magnetic response without the need for changes in external ligation. At 1.5 GPa the structure of [Mn(6)O(2)(Et-sao)(6)(O(2)CPh(Me)(2))(2)(EtOH)(6)] (1; Et-saoH(2) = 2-hydroxyphenylpropanone)--a single molecule magnet (SMM) with an effective anisotropy barrier of approximately 86 K--and of [Mn(6)O(2)(Et-sao)(6)(O(2)C-naphth)(2)(EtOH)(4)(H(2)O)(2)] 2 both undergo significant structural distortions of their metallic skeletons, which has a direct effect upon the observed magnetic response.

Synthesis and characterisation of a Ni4 single-molecule magnet with S4 symmetry.

[Ni4Cl4(HL)4] () {H2L=HN(CH2CH2OH)2} has S4 symmetry and crystallises in the tetragonal space group I4(1)/a. Two exchange couplings are observed between the four Ni(II) centres, with J1=7.29 cm(-1) and J2=-2.

Cobalt(II) citrate cubane single-molecule magnet.

An investigation of the magnetic properties of the cobalt(II) citrate cubane [C(NH 2) 3] 8{Co 4(cit) 4}.4H 2O reveals that the cluster is a new cobalt(II) single-molecule magnet, with an energy barrier to reorientation of the magnetization, Delta E/ k B = 21 K, and tau 0 = 8 x 10 (-7) s. The compound displays distinct, frequency-dependent peaks in the out-of-phase (chi'') component of the ac magnetic susceptibility and magnetization versus field hysteresis loops that are temperature and sweep rate dependent.

Effects of high pressure on the luminescence spectra of Eu(SO4)2.NH4 microcrystals: anisotropically induced structural distortions.

The possibilities of the use of Eu3+ in extracting information of the pressure effects on the nature of its crystal site in the NH4.Eu(SO4)2 catalytic host are closely inspected through the study of emission spectra for applied pressures up to 87 kbar. The phenomenological crystal field analysis of these spectra reveals clear discontinuities, at approximately 30 kbar, the sharper ones, and then at approximately 70 kbar, in crystal field strength trends, which taken together with structure-based simulations of crystal field interactions indicate well-defined pressure-induced anisotropic distortions in Eu3+ local environments.

A mixed-valence Co7 single-molecule magnet with C3 symmetry.

The synthesis, structure and magnetic properties of [Co(II)(4)Co(III)(3)(HL)(6)(NO(3))(3)(H(2)O)(3)](2+) [H(3)L = H(2)NC(CH(2)OH)(3)] are reported: the complex is an exchange-biased single molecule magnet.