New iodate fluoride Rb2Ce(IO3)5F with nonlinear optical properties.

New noncentrosymmetric cerium(IV) iodate fluoride Rb2Ce(IO3)5F was prepared employing a hydrothermal technique. The compound crystallizes in the Cmc21 space group (#36) with cell parameters a = 11.1518(6) Å, b = 8.1187(4) Å and c = 17.1581(10) Å. The crystal structure of Rb2Ce(IO3)5F consists of layers composed of 8-vertex CeO7F and 7-vertex Rb(1)O7 and Rb(2)O6F polyhedra interconnected by I(2)O3 groups. These layers are stitched by trigonal pyramidal I(1)O3 and I(3)O3 groups into a 3D framework. Synthesized iodate fluoride is thermally stable in air up to 430 °C. According to DFT calculations, Rb2Ce(IO3)5F is a direct-gap semiconductor with a band gap of ca. 2.33 eV. This value is in good agreement with an estimated optical gap value of 2.35 eV. The important feature of Rb2Ce(IO3)5F is the ability to generate a second optical harmonic signal comparable to that of KH2PO4.

Thermodynamic Properties and DFT Study on Highly Frustrated Cr3BO6: Coexistence of Spin-Singlets with Long-Range Magnetic Order.

The triangle-based magnetic subsystem of borates with the mineral norbergite structure M3BO6 (M = Fe, Cr, V) makes these compounds unique to investigate rare quantum ground states influenced by strong magnetic frustration. In this work, we investigated the thermal and magnetic properties of Cr3BO6 to find that despite very large negative Weiss temperature Θ = -160.7 K, it orders only at TN = 4.5 K and experiences a spin-flop transition at µ0H = 5 T. Density functional theory (DFT) calculations of exchange interaction parameters allow for suggesting the model of magnetic subsystem in chromium borate Cr3BO6. The results prove the decisive role of magnetic frustration on the formation of long-range order, providing therefore a basis for future study. Both experimental data and first-principles calculations point to the coexistence of chromium spin-singlets with long-range antiferromagnetic order.

Anhydrous copper tellurite disulfate Cu3TeO3(SO4)2 featuring the coexistence of spin singlets and a long-range antiferromagnetic order.

Anhydrous copper tellurite sulfate, Cu3TeO3(SO4)2, has been synthesized via vapor transport reactions in sealed silica glass ampoules. In measurements of magnetization M, magnetic susceptibility χ, specific heat Cp and X-band electron spin resonance, a long-range antiferromagnetic order at TN = 13 K and an H-T magnetic phase diagram have been established. One-third of Cu2+ ions were found to form magnetically silent dimers. A peak in dielectric permittivity ε, which accompanies the Néel order, allows considering Cu3TeO3(SO4)2 as a magnetoelectric multiferroic material of the second type. Density functional theory calculations provided estimations of leading exchange interaction parameters.

New Nabokoite-like Phases ACu7 TeO4 (SO4 )5 Cl (A=Na, K, Rb, Cs) with Decorated and Distorted Square Kagome Lattices.

A new family of compounds ACu7 TeO4 (SO4 )5 Cl (A=Na, K, Rb, Cs) isostructural to mineral Nabokoite (K species) was synthesized by solid state and gas transport reactions in sealed ampoules and characterized in measurements of magnetization and specific heat in a wide temperature range. These complex compounds are of the utmost interest as a testing playground to study the properties of quasi-two-dimensional magnets with a square kagome lattice geometry. A quantum ground state of such a corner-sharing network is a spin liquid. Unlike idealized grid analyzed in numerous models, the square kagome lattice in nabokoites is wavy and distorted being composed of versatile triangles. Moreover, it contains "excessive" decorating magnetic ions, which makes magnetism of these objects even more complicated. The interaction of these decorating ions through virtual excitations of the square kagome lattice is accompanied by the formation of a long-range magnetic order coexisting with the spin liquid.

Polytypism of Ln(SeO3)(HSeO3)·2H2O compounds: synthesis and crystal structure of the first monoclinic modification of Nd(SeO3)(HSeO3)·2H2O, DFT calculations and order/disorder description.

Compounds with the general formula Ln3+(SeO3)(HSeO3)·2H2O, where Ln = Sm3+, Tb3+, Nd3+ and Lu3+, are characterized by orthorhombic symmetry with space group P212121 and unit-cell parameters in the ranges a ∼ 6.473-6.999, b ∼ 6.845-7.101, c ∼ 16.242-16.426 Å. Light-purple irregularly shaped crystals of a new monoclinic polytype of neodymium selenite Nd(SeO3)(HSeO3)·2H2O have been obtained during a mild-condition hydrothermal synthesis. The monoclinic unit-cell parameters are: a = 7.0815 (2), b = 6.6996 (2), c = 16.7734 (5) Å, ß = 101.256 (1)°, V = 780.48 (6) Å3; space group P21/c. The crystal structures of Nd(SeO3)(HSeO3)·2H2O polymorphs show order-disorder (OD) character and can be described using the same OD groupoid family, more precisely a family of OD structures built up from two kinds of non-polar layers (category IV). The first monoclinic maximum degree order (MDO) structure (MDO1-polytype) with space group P21/c can be obtained when the inversion centre is active in the L2n-type layers, while the second MDO structure (MDO2-polytype) is orthorhombic with space group P212121 and can be obtained when the [21--] operation is active in the L2n-type layers. The structural complexity parameters and DFT calculations of both polytypes show that the polytype structures are extremely close energy-wise and almost equally viable from the point of total energy of the structure.

Magnetism of coupled spin tetrahedra in ilinskite-type KCu5O2(SeO3)2Cl3.

Synthesis, thermodynamic properties, and microscopic magnetic model of ilinskite-type KCu5O2(SeO3)2Cl3 built by corner-sharing Cu4 tetrahedra are reported, and relevant magnetostructural correlations are discussed. Quasi-one-dimensional magnetic behavior with the short-range order around 50 K is rationalized in terms of weakly coupled spin ladders (tubes) having a complex topology formed upon fragmentation of the tetrahedral network. This fragmentation is rooted in the non-trivial effect of the SeO3 groups that render the Cu-O-Cu superexchange strongly ferromagnetic even at bridging angles exceeding 110°.

Crystal structure, physical properties, and electronic and magnetic structure of the spin S = 5/2 zigzag chain compound Bi2Fe(SeO3)2OCl3.

We report the synthesis and characterization of the new bismuth iron selenite oxochloride Bi2Fe(SeO3)2OCl3. The main feature of its crystal structure is the presence of a reasonably isolated set of spin S = 5/2 zigzag chains of corner-sharing FeO6 octahedra decorated with BiO4Cl3, BiO3Cl3, and SeO3 groups. When the temperature is lowered, the magnetization passes through a broad maximum at Tmax ≈ 130 K, which indicates the formation of a magnetic short-range correlation regime. The same behavior is demonstrated by the integral electron spin resonance intensity. The absorption is characterized by the isotropic effective factor g ≈ 2 typical for high-spin Fe(3+) ions. The broadening of ESR absorption lines at low temperatures with the critical exponent ß = 7/4 is consistent with the divergence of the temperature-dependent correlation length expected for the quasi-one-dimensional antiferromagnetic spin chain upon approaching the long-range ordering transition from above. At TN = 13 K, Bi2Fe(SeO3)2OCl3 exhibits a transition into an antiferromagnetically ordered state, evidenced in the magnetization, specific heat, and Mössbauer spectra. At T < TN, the (57)Fe Mössbauer spectra reveal a low saturated value of the hyperfine field Hhf ≈ 44 T, which indicates a quantum spin reduction of spin-only magnetic moment ΔS/S ≈ 20%. The determination of exchange interaction parameters using first-principles calculations validates the quasi-one-dimensional nature of magnetism in this compound.

Crystal structures and variable magnetism of PbCu2(XO3)2Cl2 with X = Se, Te.

Novel Cu(2+)-based compounds PbCu2(SeO3)2Cl2 (space group C2/c; a = 13.056(1) Å; b = 9.5567(9) Å; c = 6.9006(6) Å; ß = 90.529(7)°; RI = 0.0371) and PbCu2(TeO3)2Cl2 (space group P2(1); a = 7.2401(2) Å; b = 7.2688(2) Å; c = 8.2846(2) Å; ß = 96.416(2)°; R(I) = 0.0570) have been obtained by solid-state synthesis. Their crystal structures are remarkably dissimilar and underlie a very different magnetic behavior. While PbCu2(SeO3)2Cl2 can be well described by a spin-chain model with an exchange coupling of J1 ≃ 160 K, PbCu2(TeO3)2Cl2 is a spin-dimer system that, however, features a comparable magnetic nearest-neighbor coupling of J ≃ 213 K. PbCu2(SeO3)2Cl2 orders antiferromagnetically below 12 K, whereas PbCu2(TeO3)2Cl2 lacks long-range magnetic order down to at least 2 K, owing to the strong dimerization of the Cu(2+) spins. Crystal structures of both compounds are rationalized in terms of relevant magnetic exchange pathways, and the implications for a broader range of Cu(2+) compounds are discussed.

Cs7Nd11(SeO3)12Cl16: first noncentrosymmetric structure among alkaline-metal lanthanide selenite halides.

Cs7Nd11(SeO3)12Cl16, the complex selenite chloride of cesium and neodymium, was synthesized in the NdOCl-SeO2-CsCl system. The compound has been characterized using single-crystal X-ray diffraction, electron diffraction, transmission electron microscopy, luminescence spectroscopy, and second-harmonic-generation techniques. Cs7Nd11(SeO3)12Cl16 crystallizes in an orthorhombic unit cell with a = 15.911(1) Å, b = 15.951(1) Å, and c = 25.860(1) Å and a noncentrosymmetric space group Pna2(1) (No. 33). The crystal structure of Cs7Nd11(SeO3)12Cl16 can be represented as a stacking of Nd11(SeO3)12 lamellas and CsCl-like layers. Because of the layered nature of the Cs7Nd11(SeO3)12Cl16 structure, it features numerous planar defects originating from occasionally missing the CsCl-like layer and violating the perfect stacking of the Nd11(SeO3)12 lamellas. Cs7Nd11(SeO3)12Cl16 represents the first example of a noncentrosymmetric structure among alkaline-metal lanthanide selenite halides. Cs7Nd11(SeO3)12Cl16 demonstrates luminescence emission in the near-IR region with reduced efficiency due to a high concentration of Nd(3+) ions causing nonradiative cross-relaxation.