(CN3H6)[FeIIFeIII(SO4)3(H2O)3]: A Framework Iron Sulfate with a Mixed S = 2 and S = 5/2 Honeycomb Lattice.

A new guanidinium-templated hydrated iron sulfate, [CN3H6][FeIIFeIII(SO4)3(H2O)3] (1), was prepared from strongly acidic aqueous solutions. Its crystal structure is comprised from FeIIIO6 and FeIIO3(H2O)3 octahedra linked by sulfate bridges forming a [FeIIFeII(SO4)3(H2O)3]- 3D framework with a layer-by-layer ordering of ferric and ferrous cations. The structural topology of the framework is related to the anhydrous rhombohedral mikasaite Fe2(SO4)3. The removal of part of the sulfate tetrahedra and the partial replacement of the Fe3+ cations in the [Fe3+2(SO4)3]0 framework by Fe2+ provide a negative charge and allow the incorporation of the protonated organic species in the voids. The compound 1 has been characterized by single-crystal X-ray diffraction, TG and DSC analyses, UV-vis-NIR spectroscopy, magnetic susceptibility, Mössbauer spectroscopy, IR and Raman spectroscopy, and density functional band-structure calculations. The magnetic behavior of 1 shows an interplay of FeII (S = 2) and FeIII (S = 5/2) sublattices that exhibit different types of antiferromagnetic couplings, one FeIII-FeIII (J1 ∼ 6.1 K) and two FeII-FeIII couplings (J2 ∼ 1 K, J3 ∼ 5.9 K) within corrugated honeycomb layers. These ferrimagnetic layers are coupled antiparallel to each other, resulting in an overall antiferromagnetic order below TN = 31 K.

Effect of antifluorite layer on the magnetic order in Eu-based 1111 compounds, EuTAsF (T = Zn, Mn, and Fe).

The 1111 compounds with an alternating sequence of fluorite and antifluorite layers serve as structural hosts for the vast family of Fe-based superconductors. Here, we use neutron powder diffraction and density-functional-theory (DFT) band-structure calculations to study magnetic order of Eu2+ in the [EuF]+ fluorite layers depending on the nature of the [TAs]- antifluorite layer that can be non-magnetic semiconducting (T = Zn), magnetic semiconducting (T = Mn), or magnetic metallic (T = Fe). Antiferromagnetic transitions at TN ∼ 2.4-3 K due to an ordering of the Eu2+ magnetic moments were confirmed in all three EuTAsF compounds. Whereas in EuTAsF (T = Zn and Mn), the commensurate k1 = (½ ½ 0) stripe order pattern with magnetic moments within the a-b plane is observed, the order in EuFeAsF is incommensurate with k = (0 0.961(1) ½) and represents a cycloid of Eu2+ magnetic moments confined within the bc-plane. Additionally, the Mn2+ sublattice in EuMnAsF features a robust G-type antiferromagnetic order that persists at least up to room temperature, with magnetic moments along the c-direction. Although DFT calculations suggest stripe antiferromagnetic order in the Fe-sublattice of EuFeAsF as the ground state, neutron diffraction reveals no evidence of long-range magnetic order associated with Fe. We show that the frustrating interplane interaction J3 between the adjacent [EuF]+ layers is comparable with in-plane J1-J2 interactions already in the case of semiconducting fluorite layers [TAs]- (T = Zn and Mn) and becomes dominant in the case of the metallic [FeAs]- ones. The latter, along with a slight orthorhombic distortion, is proposed to be the origin of the incommensurate magnetic structure observed in EuFeAsF.

Semiconducting and Metallic Compounds within the IrIn3 Structure Type: Stability and Chemical Bonding.

Narrow-gap semiconductors are very rare among intermetallic compounds. They appear only when two factors come together: strong hybridization of valence orbitals in the vicinity of the Fermi level and an appropriate number of valence electrons. Surprisingly, the IrIn3 family of intermetallics contains a number of semiconductors, including 17 e- FeGa3, RuGa3, OsGa3, and RuIn3, for which the d-p hybridization gap opens at the Fermi energy. We present comprehensive total energy electronic-structure calculations and crystal orbital Hamilton population analysis of the stable IrIn3-type compounds with semiconducting and metallic properties. The calculated electronic structures possess two pseudogaps and one real gap at the magic valence electron count of 15, 17, and 18 e- per formula unit. When the Fermi level is located in these gaps, the antibonding states are minimized. Total energies calculated for the isomorphous compounds suggest that the metallic state with 18 e- leads to a comparable or even higher thermodynamic stability than the semiconducting state with 17 e-.

Chemical Vapor Transport Synthesis of Cu(VO)2(AsO4)2 With Two Distinct Spin-1/2 Magnetic Ions.

A new copper vanadyl arsenate, Cu(VO)2(AsO4)2, was synthesized via the chemical vapor transport method. Cu(VO)2(AsO4)2 adopts an original structure type. It is characterized by layers formed by edge-sharing and corner-sharing V-centered octahedra resulting in a unique topology that was hitherto not reported for vanadates. Single CuO6 octahedra connect vanadate layers into a rigid framework. The thermal expansion of the framework studied by the single-crystal HT X-ray diffraction is reported. The magnetic behavior of Cu(VO)2(AsO4)2 shows an interplay of ferromagnetic V4+-V4+ and antiferromagnetic Cu2+-V4+ interactions that result in a ferrimagnetic long-range order below TC = 66 K.

From (S = 1) Spin Hexamer to Spin Tetradecamer by CuO Interstitials in A2Cu3O(CuO)x(SO4)3 (A = alkali).

(Na,K)2Cu3O(SO4)3 compounds form structural chains of Cu6 hexameric units with nominal S = 1 spins due to the interplay between inner strong antiferromagnetic and ferromagnetic exchanges. We show here that the lattice relaxation after the replacement of alkali by larger Rb and Cs ones is accompanied by the insertion of neutral CuO species into (Rb,Cs)2Cu3O(CuO)x(SO4)3 phases. Structurally, interstitial CuO links the next two Cu6 units in longer Cu14 tetradecameric ones. For A = Cs (x = 0.5), the cationic ordering is perfect inside a double-cell superstructure. Magnetically, the original Cu14 units consist of frustrated fragments of an S = 1/2 spin ladder, with ferromagnetic rung-like but antiferromagnetic leg-like and next-nearest neighbor couplings. It returns S = 1 Cu14 spin clusters, effective around 100 K. Our density functional theory calculations and susceptibility fits also show that at low temperatures they interact in two-dimensional lattices, despite the existence of short inter-Cu-Cu distances between the next two clusters along pseudo-one-dimensional chains.

Synthesis of Ilmenite-type ε-Mn2O3 and Its Properties.

In contrast to the corundum-type A2X3 structure, which has only one crystallographic site available for trivalent cations (e.g., in hematite), the closely related ABX3 ilmenite-type structure comprises two different octahedrally coordinated positions that are usually filled with differently charged ions (e.g., in Fe2+Ti4+O3 ilmenite). Here, we report a synthesis of the first binary ilmenite-type compound fabricated from a simple transition-metal oxide (Mn2O3) at high-pressure high-temperature (HP-HT) conditions. We experimentally established that, at normal conditions, the ilmenite-type Mn2+Mn4+O3 (ε-Mn2O3) is an n-type semiconductor with an indirect narrow band gap of Eg = 0.55 eV. Comparative investigations of the electronic properties of ε-Mn2O3 and previously discovered quadruple perovskite ζ-Mn2O3 phase were performed using X-ray absorption near edge spectroscopy. Magnetic susceptibility measurements reveal an antiferromagnetic ordering in ε-Mn2O3 below 210 K. The synthesis of ε-Mn2O3 indicates that HP-HT conditions can induce a charge disproportionation in simple transition-metal oxides A2O3, and potentially various mixed-valence polymorphs of these oxides, for example, with ilmenite-type, LiNbO3-type, perovskite-type, and other structures, could be stabilized at HP-HT conditions.

Structural Stability and Properties of Marokite-Type γ-Mn3O4.

We synthesized single crystals of marokite (CaMn2O4)-type orthorhombic manganese (II,III) oxide, γ-Mn3O4, in a multianvil apparatus at pressures of 10-24 GPa. The magnetic, electronic, and optical properties of the crystals were investigated at ambient pressure. It was found that γ-Mn3O4 is a semiconductor with an indirect band gap Eg of 0.96 eV and two antiferromagnetic transitions (TN) at ∼200 and ∼55 K. The phase stability of the γ-Mn3O4 crystals was examined in the pressure range of 0-60 GPa using single-crystal X-ray diffraction and Raman spectroscopy. A bulk modulus of γ-Mn3O4 was determined to be B0 = 235.3(2) GPa with B' = 2.6(6). The γ-Mn3O4 phase persisted over the whole pressure range studied and did not transform or decompose upon laser heating of the sample to ∼3500 K at 60 GPa. This result seems surprising, given the high-pressure structural diversity of iron oxides with similar stoichiometries. With an increase in pressure, the degree of distortion of MnO6 polyhedra decreased. Furthermore, there are signs indicating a limited charge transfer between the Mn3+ ions in the octahedra and the Mn2+ ions in the trigonal prisms. Our results demonstrate that the high-pressure behavior of the structural, electronic, and chemical properties of manganese oxides strongly differs from that of iron oxides with similar stoichiometries.

Two Linear Regimes in Optical Conductivity of a Type-I Weyl Semimetal: The Case of Elemental Tellurium.

Employing high-pressure infrared spectroscopy we unveil the Weyl semimetal phase of elemental Te and its topological properties. The linear frequency dependence of the optical conductivity provides clear evidence for metallization of trigonal tellurium (Te-I) and the linear band dispersion above 3.0 GPa. This semimetallic Weyl phase can be tuned by increasing pressure further: a kink separates two linear regimes in the optical conductivity (at 3.7 GPa), a signature proposed for Type-II Weyl semimetals with tilted cones; this however reveals a different origin in trigonal tellurium. Our density-functional calculations do not reveal any significant tilting and suggest that Te-I remains in the Type-I Weyl phase, but with two valence bands in the vicinity of the Fermi level. Their interplay gives rise to the peculiar optical conductivity behavior with more than one linear regime. Pressure above 4.3 GPa stabilizes the more complex Te-II and Te-III polymorphs, which are robust metals.

Cu9O2(VO4)4Cl2, the First Copper Oxychloride Vanadate: Mineralogically Inspired Synthesis and Magnetic Behavior.

A new spin-1/2 frustrated antiferromagnet, Cu9O2(VO4)4Cl2, was synthesized via chemical vapor transport method that emulates mineral formation in volcanic fumaroles. Cu9O2(VO4)4Cl2 is the first copper oxychloride vanadate obtained in the ternary CuO-V2O5-CuCl2 anhydrous system. Copper ions constitute a three-dimensional complex framework with a topological structure novel for synthetic compounds but similar to that in the fumarolic mineral yaroshevskite. All of the oxygen atoms except for the O7 site are strongly bonded in the VO4 tetrahedra. The O7 site belongs to an additional oxygen atom (Oa) being tetrahedrally coordinated by four Cu atoms, thus forming the OCu4 tetrahedra. The structural formula can be represented as Cu3[Cu6O2](VO4)4Cl2 highlighting oxocentered units in the structure. IR spectra reveal several absorption bands at 526, 578, and 601 cm-1 interpreted as a characteristic feature of the OCu4 tetrahedra. Cu9O2(VO4)4Cl2 reveals ferrimagnetic behavior with the Curie temperature TC = 24 K and the uncompensated moment of Mr ∼ 1.9 µB/f.u.

A Room-Temperature Verwey-type Transition in Iron Oxide, Fe5 O6.

Functional oxides whose physicochemical properties may be reversibly changed at standard conditions are potential candidates for the use in next-generation nanoelectronic devices. To date, vanadium dioxide (VO2 ) is the only known simple transition-metal oxide that demonstrates a near-room-temperature metal-insulator transition that may be used in such appliances. In this work, we synthesized and investigated the crystals of a novel mixed-valent iron oxide with an unconventional Fe5 O6 stoichiometry. Near 275 K, Fe5 O6 undergoes a Verwey-type charge-ordering transition that is concurrent with a dimerization in the iron chains and a following formation of new Fe-Fe chemical bonds. This unique feature highlights Fe5 O6 as a promising candidate for the use in innovative applications. We established that the minimal Fe-Fe distance in the octahedral chains is a key parameter that determines the type and temperature of charge ordering. This model provides new insights into charge-ordering phenomena in transition-metal oxides in general.

Rearrangement of Uncorrelated Valence Bonds Evidenced by Low-Energy Spin Excitations in YbMgGaO_{4}.

dc-magnetization data measured down to 40 mK speak against conventional freezing and reinstate YbMgGaO_{4} as a triangular spin-liquid candidate. Magnetic susceptibility measured parallel and perpendicular to the c axis reaches constant values below 0.1 and 0.2 K, respectively, thus indicating the presence of gapless low-energy spin excitations. We elucidate their nature in the triple-axis inelastic neutron scattering experiment that pinpoints the low-energy (E≤J_{0}∼0.2 meV) part of the excitation continuum present at low temperatures (TJ_{0} that is rooted in the breaking of nearest-neighbor valence bonds and persists to temperatures well above J_{0}/k_{B}, the low-energy one originates from the rearrangement of the valence bonds and thus from the propagation of unpaired spins. We further extend this picture to herbertsmithite, the spin-liquid candidate on the kagome lattice, and argue that such a hierarchy of magnetic excitations may be a universal feature of quantum spin liquids.

Crystal Growth of Intermetallics from the Joint Flux: Exploratory Synthesis through the Control of Valence Electron Count.

In this study, we modify the flux-growth method for the purpose of exploratory synthesis of ternary intermetallic compounds. Our concept is based on the assumption that valence electron count plays a crucial role in the stability of polar intermetallic compounds of different structure types. Control of the valence electron count parameter is made possible through the use of an excess of two metals having a different number of valence electrons. By gradually changing the ratio between these metals in the joint flux, we scan the gross number of valence electrons and explore the crystallization of new compounds. In the ternary system Re-Ga-Zn, we detect compounds belonging to three structure types, ReGa5, PtHg4, and V8Ga41, while gradually increasing the content of Zn metal in the flux. Two new compounds, ReGa3Zn and Re8Ga41- xZn x with x = 21.2(5), are obtained in the form of high-quality single crystals, and the former compound shows the narrow-gap semiconducting behavior favorable for high thermoelectric performance.

Crystal Structures and Low-Dimensional Ferromagnetism of Sodium Nickel Phosphates Na5Ni2(PO4)3·H2O and Na6Ni2(PO4)3OH.

Two new sodium nickel phosphates, Na5Ni2(PO4)3·H2O (I) and Na6Ni2(PO4)3OH (II), have been synthesized hydrothermally and characterized by synchrotron X-ray diffraction, electron diffraction, low-temperature thermodynamic and magnetic measurements, and ab initio calculations. Unlike the majority of Ni2+ compounds, I and II show predominant ferromagnetic exchange couplings. I crystallizes in the monoclinic space group P21/ n ( a = 14.0395(4) Å, b = 5.1847(14) Å, c = 16.4739(4) Å, ß = 110.4186(14)°) and features chains of ferromagnetically coupled Ni2+ ions. In II with the orthorhombic space group Pcmb ( a = 7.5007(15) Å, b = 21.4661(4) Å, c = 7.1732(15) Å), the ferromagnetically coupled Ni2+ ions form dimers arranged on a spin ladder. Both compounds represent rare examples of quasi-one-dimensional ferromagnets. Structural features behind this unusual magnetic behavior are discussed.

Endohedral Cluster Superconductors in the Mo-Ga-Sn System Explored by the Joint Flux Technique.

Endohedral Ga cluster compounds feature nontrivial superconducting states including the two-gap superconductivity similar in nature to MgB2. We use the joint flux synthetic technique to introduce Sn into the Ga matrix and tune the valence electron count in the two new endohedral cluster superconductors Mo8Ga41-xSnx and Mo4Ga21-x-δSnx with critical temperatures of Tc = 8.7 and 5.85 K, respectively. While the former compound is a derivative of the previously known Mo8Ga41 superconductor, where Sn atoms are enclosed inside the Sn@Ga6 octahedral clusters, the latter is a new architecture built upon Mo@Ga9Sn clusters, Ga@Ga12 cuboctahedra, and Sn4 squares. We show that this novel Mo4Ga21-x-δSnx superconductor features strong electron-phonon coupling with the large ratio of 2Δ(0)/(kBTc) = 4.1 similar to that of the Mo8Ga41 superconductor with the closely related crystal structure.

Compressibility of BiCu2PO6: Polymorphism against S = 1/2 Magnetic Spin Ladders.

BiCu2PO6 is a unique example of a S = 1/2 ladder where the magnetic exchanges are mainly confined in 1D ∞[BiCu2O2]3+ cationic ribbons, although the shortest Cu-Cu separation between them exists. Its original magnetic topology gives the most representative example of a frustrated quantum ladder to investigate the complex physics behind it. Herein, we report the synthesis and characterization of one high-pressure polymorph. In this new phase, the preservation of 1D ∞[BiCu2O2]3+ units somewhat restacked leads to the preservation of its gapped magnetic ground state and ladder topology. The comparison of both compounds highlights the start of a thermodynamic conjuncture, where both the stable ambient-pressure (AP) and metastable high-pressure (HP) forms display the same equilibrium volume and superposed volume dependence of the energy, leading to a first-order AP → HP transition undetected by differential thermal analysis.

Pressure dependence of spin canting in ammonium metal formate antiferromagnets.

High-pressure single-crystal X-ray diffraction at ambient temperature and high-pressure SQUID measurements down to 2 K were performed up to ∼2.5 GPa on ammonium metal formates, [NH4][M(HCOO)3] where M = Mn2+, Fe2+, and Ni2+, in order to correlate structural variations to magnetic behaviour. Similar structural distortions and phase transitions were observed for all compounds, although the transition pressures varied with the size of the metal cation. The antiferromagnetic ordering in [NH4][M(HCOO)3] compounds was maintained as a function of pressure, and the magnetic ordering transition temperature changed within a few kelvins depending on the structural distortion and the metal cation involved. These compounds, in particular [NH4][Fe(HCOO)3], showed greatest sensitivity to the degree of spin canting upon compression, clearly visible from the twenty-fold increase in the low-temperature magnetisation for [NH4][Fe(HCOO)3] at 1.4 GPa, and the change from purely antiferromagnetic to weakly ferromagnetic ordering in [NH4][Mn(HCOO)3] at 1 GPa. The variation in the exchange couplings and spin canting was checked with density-functional calculations that reproduce well the increase in canted moment within [NH4][Fe(HCOO)3] upon compression, and suggest that the Dzyaloshinskii-Moriya (DM) interaction is evolving as a function of pressure. The pressure dependence of spin canting is found to be highly dependent on the metal cation, as magnetisation magnitudes did not change significantly for when M = Ni2+ or Mn2+. These results demonstrate that the overall magnetic behaviour of each phase upon compression was not only dependent on the structural distortions but also on the electronic configuration of the metal cation.

Crystalline Electric-Field Randomness in the Triangular Lattice Spin-Liquid YbMgGaO_{4}.

We apply moderate-high-energy inelastic neutron scattering (INS) measurements to investigate Yb^{3+} crystalline electric field (CEF) levels in the triangular spin-liquid candidate YbMgGaO_{4}. Three CEF excitations from the ground-state Kramers doublet are centered at the energies ℏω=39, 61, and 97 meV in agreement with the effective spin-1/2 g factors and experimental heat capacity, but reveal sizable broadening. We argue that this broadening originates from the site mixing between Mg^{2+} and Ga^{3+} giving rise to a distribution of Yb-O distances and orientations and, thus, of CEF parameters that account for the peculiar energy profile of the CEF excitations. The CEF randomness gives rise to a distribution of the effective spin-1/2 g factors and explains the unprecedented broadening of low-energy magnetic excitations in the fully polarized ferromagnetic phase of YbMgGaO_{4}, although a distribution of magnetic couplings due to the Mg/Ga disorder may be important as well.

Structural and Magnetic Transitions in CaCo3V4O12 Perovskite at Extreme Conditions.

We investigated the structural, vibrational, magnetic, and electronic properties of the recently synthesized CaCo3V4O12 double perovskite with the high-spin (HS) Co2+ ions in a square-planar oxygen coordination at extreme conditions of high pressures and low temperatures. The single-crystal X-ray diffraction and Raman spectroscopy studies up to 60 GPa showed a conservation of its cubic crystal structure but indicated a crossover near 30 GPa. Above 30 GPa, we observed both an abnormally high "compressibility" of the Co-O bonds in the square-planar oxygen coordination and a huge anisotropic displacement of HS-Co2+ ions in the direction perpendicular to the oxygen planes. Although this effect is reminiscent of a continuous HS → LS transformation of the Co2+ ions, it did not result in the anticipated shrinkage of the cell volume because of a certain "stiffing" of the bonds of the Ca and V cations. We verified that the oxidation states of all the cations did not change across this crossover, and hence, no charge-transfer effects were involved. Consequently, we proposed that CaCo3V4O12 could undergo a phase transition at which the large HS-Co2+ ions were pushed out of the oxygen planes because of lattice compression. The antiferromagnetic transition in CaCo3V4O12 at 100 K was investigated by neutron powder diffraction at ambient pressure. We established that the magnetic moments of the Co2+ ions were aligned along one of the cubic axes, and the magnetic structure had a 2-fold periodicity along this axis, compared to the crystallographic one.

Muon Spin Relaxation Evidence for the U(1) Quantum Spin-Liquid Ground State in the Triangular Antiferromagnet YbMgGaO_{4}.

Muon spin relaxation (µSR) experiments on single crystals of the structurally perfect triangular antiferromagnet YbMgGaO_{4} indicate the absence of both static long-range magnetic order and spin freezing down to 0.048 K in a zero field. Below 0.4 K, the µ^{+} spin relaxation rates, which are proportional to the dynamic correlation function of the Yb^{3+} spins, exhibit temperature-independent plateaus. All these µSR results unequivocally support the formation of a gapless U(1) quantum spin liquid ground state in the triangular antiferromagnet YbMgGaO_{4}.

Nontrivial Recurrent Intergrowth Structure and Unusual Magnetic Behavior of Intermetallic Compound Fe32+δGe33As2.

A new phase Fe32+δGe33As2 (δ ≤ 0.136) was obtained by two-step synthesis from the elements. Fe32+δGe33As2 crystallizes in its own structure type (space group P6/mmm, Z = 1, a = 11.919(3) Å, c = 7.558(4) Å) that can be described as a recurrent two-dimensional intergrowth of two intermetallic structure types, MgFe6Ge6 and Co2Al5. Their blocks are represented by infinite columns in the structure. No visible structural changes were observed in the temperature range from 10 to 300 K. At 125 K, Fe32+δGe33As2 undergoes an antiferromagnetic-like transition, while above 150 K it shows a typical Curie-Weiss paramagnetic behavior. Below the transition temperature, a peculiar field-dependent magnetic susceptibility, that shows a significant increase of the susceptibility upon increasing the magnetic field, and a change in transport properties have been observed. Above 140 K, Fe32+δGe33As2 reveals a metallic behavior, in agreement with electronic structure calculation, while below this point the resistivity nonmonotonically increases upon cooling. The Seebeck coefficient is positive, indicating that holes are the major charge carriers, and shows a broad maximum around 57 K.