High- versus Low-Spin Ni2+ in Elongated Octahedral Environments: Sr2NiO2Cu2Se2, Sr2NiO2Cu2S2, and Sr2NiO2Cu2(Se1-x S x )2.

Sr2NiO2Cu2Se2, comprising alternating [Sr2NiO2]2+ and [Cu2Se2]2- layers, is reported. Powder neutron diffraction shows that the Ni2+ ions, which are in a highly elongated NiO4Se2 environment with D4h symmetry, adopt a high-spin configuration and carry localized magnetic moments which order antiferromagnetically below ∼160 K in a √2a × âˆš2a × 2c expansion of the nuclear cell with an ordered moment of 1.31(2) µB per Ni2+ ion. The adoption of the high-spin configuration for this d 8 cation in a pseudo-square-planar ligand field is supported by consideration of the experimental bond lengths and the results of density functional theory (DFT) calculations. This is in contrast to the sulfide analogue Sr2NiO2Cu2S2, which, according to both experiment and DFT calculations, has a much more elongated ligand field, more consistent with the low-spin configuration commonly found for square-planar Ni2+, and accordingly, there is no evidence for magnetic moment on the Ni2+ ions. Examination of the solid solution Sr2NiO2Cu2(Se1-x S x )2 shows direct evidence from the evolution of the crystal structure and the magnetic ordering for the transition from high-spin selenide-rich compounds to low-spin sulfide-rich compounds as a function of composition. Compression of Sr2NiO2Cu2Se2 up to 7.2 GPa does not show any structural signature of a change in the spin state. Consideration of the experimental and computed Ni2+ coordination environments and their subtle changes as a function of temperature, in addition to transitions evident in the transport properties and magnetic susceptibilities in the end members, Sr2NiO2Cu2Se2 and Sr2NiO2Cu2S2, suggest that simple high-spin and low-spin models for Ni2+ may not be entirely appropriate and point to further complexities in these compounds.

Frustration and Glasslike Character in RIn1- xMn xO3 (R = Tb, Dy, Gd).

We bring together ac susceptibility and dc magnetization to uncover the rich magnetic field-temperature behavior of a series of rare earth indium oxides, RInO3 (R = Tb, Dy, and Gd). The degree of frustration is much larger than expected, particularly in TbInO3, and the ground states are glasslike with antiferromagnetic tendencies. The activation energy for spin reorientation is low. Chemical substitution with Mn3+ ions to form TbIn1- xMn xO3 ( x ≤ 0.01) relieves much of the frustration that characterizes the parent compound and slightly enhances the short-range antiferromagnetic order. The phase diagrams developed from this work reveal the rich competition between spin orders and provide an opportunity to compare the dynamics in the RInO3 and Mn-substituted systems. These structure-property relations may be useful for understanding magnetism in other geometrically frustrated multiferroics.

Doped Sr2FeIrO6-Phase Separation and a Jeff ≠ 0 State for Ir5.

High-resolution synchrotron X-ray and neutron powder diffraction data demonstrate that, in contrast to recent reports, Sr2FeIrO6 adopts an I1̅ symmetry double perovskite structure with an a-b-c- tilting distortion. This distorted structure does not tolerate cation substitution, with low levels of A-site (Ca, Ba, La) or Fe-site (Ga) substitution leading to separation into two phases: a stoichiometric I1̅ phase and a cation-substituted, P21/ n symmetry, a-a-c+ distorted double perovskite phase. Magnetization, neutron diffraction, and 57Fe Mössbauer data show that, in common with Sr2FeIrO6, the cation substituted Sr2- xA xFe1- yGa yIrO6 phases undergo transitions to type-II antiferromagnetically ordered states at TN ∼ 120 K. However, in contrast to stoichiometric Sr2FeIrO6, cation substituted samples exhibit a further magnetic transition at TA ∼ 220 K, which corresponds to the ordering of Jeff ≠ 0 Ir5+ centers in the cation-substituted, P21/ n symmetry, double perovskite phases.

Implications of bond disorder in a S=1 kagome lattice.

Strong hydrogen bonds such as F···H···F offer new strategies to fabricate molecular architectures exhibiting novel structures and properties. Along these lines and, to potentially realize hydrogen-bond mediated superexchange interactions in a frustrated material, we synthesized [H2F]2[Ni3F6(Fpy)12][SbF6]2 (Fpy = 3-fluoropyridine). It was found that positionally-disordered H2F+ ions link neutral NiF2(Fpy)4 moieties into a kagome lattice with perfect 3-fold rotational symmetry. Detailed magnetic investigations combined with density-functional theory (DFT) revealed weak antiferromagnetic interactions (J ~ 0.4 K) and a large positive-D of 8.3 K with ms = 0 lying below ms = ±1. The observed weak magnetic coupling is attributed to bond-disorder of the H2F+ ions which leads to disrupted Ni-F···H-F-H···F-Ni exchange pathways. Despite this result, we argue that networks such as this may be a way forward in designing tunable materials with varying degrees of frustration.

The Parent Li(OH)FeSe Phase of Lithium Iron Hydroxide Selenide Superconductors.

Lithiation of hydrothermally synthesized Li1-xFex(OH)Fe1-ySe turns on high-temperature superconductivity when iron ions are displaced from the hydroxide layers by reductive lithiation to fill the vacancies in the iron selenide layers. Further lithiation results in reductive iron extrusion from the hydroxide layers, which turns off superconductivity again as the stoichiometric composition Li(OH)FeSe is approached. The results demonstrate the twin requirements of stoichiometric FeSe layers and reduction of Fe below the +2 oxidation state as found in several iron selenide superconductors.

Octanuclear Heterobimetallic {Ni4Ln4} Assemblies Possessing Ln4 Square Grid [2 × 2] Motifs: Synthesis, Structure, and Magnetism.

Octanuclear heterobimetallic complexes, [Ln4Ni4(H3L)4(µ3-OH)4(µ2-OH)4]4Cl·xH2O·yCHCl3 (Dy(3+), x = 30.6, y = 2 (1); Tb(3+), x = 28, y = 0 (2) ; Gd(3+), x = 25.3, y = 0 (3); Ho(3+), x = 30.6, y = 3 (4)) (H5L = N1,N3-bis(6-formyl-2-(hydroxymethyl)-4-methylphenol)diethylenetriamine) are reported. These are assembled by the cumulative coordination action of four doubly deprotonated compartmental ligands, [H3L](2-), along with eight exogenous -OH ligands. Within the core of these complexes, four Ln(3+)'s are distributed to the four corners of a perfect square grid while four Ni(2+)'s are projected away from the plane of the Ln4 unit. Each of the four Ni(2+)'s possesses distorted octahedral geometry while all of the Ln(3+)'s are crystallographically equivalent and are present in an elongated square antiprism geometry. The magnetic properties of compound 3 are dominated by an easy-plane single-ion anisotropy of the Ni(2+) ions [DNi = 6.7(7) K] and dipolar interactions between Gd(3+) centers. Detailed ac magnetometry reveals the presence of distinct temperature-dependent out-of-phase signals for compounds 1 and 2, indicative of slow magnetic relaxation. Magnetochemical analysis of complex 1 implies the 3d and the 4f metal ions are engaged in ferromagnetic interactions with SMM behavior, while dc magnetometry of compound 2 is suggestive of an antiferromagnetic Ni-Tb spin-exchange with slow magnetic relaxation due to a field-induced level crossing. Compound 4 exhibits an easy-plane single-ion anisotropy for the Ho(3+) ions and weak interactions between spin centers.

Heterometallic trinuclear {CoLn(III)} (Ln = Gd, Tb, Ho and Er) complexes in a bent geometry. Field-induced single-ion magnetic behavior of the Er(III) and Tb(III) analogues.

Through the use of a multi-site compartmental ligand, 2-methoxy-6-[{2-(2-hydroxyethylamino)ethylimino}methyl]phenol (LH3), the family of heterometallic, trinuclear complexes of the formula [CoLn(L)2(µ-O2CCH3)2(H2O)3]·NO3·xMeOH·yH2O has been expanded beyond Ln = Dy(III) to include Gd(III) (), Tb(III) (), Ho(III) () and Er(III) () for , and (x = 1; y = 1) and for (x = 0; y = 2). The metallic core of these complexes consists of a (Co(III)-Ln(III)-Co(III)) motif bridged in a bent geometry resulting in six-coordinated distorted Co(III) octahedra and nine-coordinated Ln(III) monocapped square-antiprisms. The magnetic characterization of these compounds reveals the erbium and terbium analogues to display a field induced single-ion magnetic behavior similar to the dysprosium analogue but at lower temperatures. The energy barrier for the reversal of the magnetization of the CoTb(III) analogue is Ueff ≥ 15.6(4) K, while for the CoEr(III) analogue Ueff ≥ 9.9(8) K. The magnetic properties are discussed in terms of distortions of the 4f electron cloud.

Synthesis and properties of lanthanide ruthenium(III) oxide perovskites.

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.

Quantifying magnetic exchange in doubly-bridged Cu-X(2)-Cu (X = F, Cl, Br) chains enabled by solid state synthesis of CuF(2)(pyrazine).

Solid state techniques involving pressure and temperature have been used to synthesize the fluoride member of the CuX(2)(pyrazine) (X = F, Cl, Br) family of coordination polymers that cannot be crystallized by solution methods. CuF(2)(pyrazine) exhibits unique trans doubly-bridged Cu-F(2)-Cu chains that provide an opportunity to quantify magnetic superexchange in an isostructural Cu-X(2)-Cu series.