Simon Cassidy

Abstract:

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 NiO4Se2environment with D4hsymmetry, adopt a high-spin configuration and carry localized magnetic moments which order antiferromagnetically below 160 K in a 2a × 2a × 2c expansion of the nuclear cell with an ordered moment of 1.31(2) μBper Ni2+ion. The adoption of the high-spin configuration for this d8cation 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-xSx)2shows 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 Sr2NiO2Cu2Se2up 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, Sr2NiO2Cu2Se2and 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.

Abstract:

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 D_4h symmetry, adopt a high-spin configuration and carry localized magnetic moments which order antiferromagnetically below ∼160 K in a √2a × √2a × 2c expansion of the nuclear cell with an ordered moment of 1.31(2) μ_B per Ni²⁺ ion. The adoption of the high-spin configuration for this d⁸ 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(Se_1–xS_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.

Abstract:

Intercalation of alkali and alkaline earth metals into ZrSe3 via soft chemical routes injects electrons and has a significant effect on the selenide-selenide bonding. K, Rb and Cs intercalates of ZrSe3 prepared at low temperatures (-78 °C) from metal ammonia solutions contrast with related polymorphs obtained at high temperature (850 °C). KxZrSe3 synthesised at low temperatures crystallises in orthorhombic Cmc21, while the polymorph obtained at high temperatures crystallises in Immm. The two structures prepared under drastically different conditions differ by relative shifting of ZrSe3 layers. In contrast, CsxZrSe3 shows the Immm polymorph at low temperature and the Cmc21 polymorph at high temperatures, while a single RbxZrSe3 polymorph in Immm is formed at both temperatures. Intercalation of Ca from liquid ammonia facilitates the co-intercalation of the solvent because of the strong solvation of Ca2+ . This compound has severe faulting due to the flexibility in the relative shifts of adjacent ZrSe3 layers.

Abstract:

We report the synthesis, crystal structure, thermal response, and electrochemical behavior of the Prussian blue analogue (PBA) K2Cu[Fe(CN)6]. From a structural perspective, this is the most complex PBA yet characterized: its triclinic crystal structure results from an interplay of cooperative Jahn–Teller order, octahedral tilts, and a collective “slide” distortion involving K-ion displacements. These different distortions give rise to two crystallographically distinct K-ion channels with different mobilities. Variable-temperature X-ray powder diffraction measurements show that K-ion slides are the lowest-energy distortion mechanism at play, as they are the only distortion to be switched off with increasing temperature. Electrochemically, the material operates as a K-ion cathode with a high operating voltage and an improved initial capacity relative to higher-vacancy PBA alternatives. On charging, K+ ions are selectively removed from a single K-ion channel type, and the slide distortions are again switched on and off accordingly. We discuss the functional importance of various aspects of structural complexity in this system, placing our discussion in the context of other related PBAs.

Abstract:

In the dense metal-organic framework Na[Mn(HCOO)3], Mn2+ ions (S=5/2) occupy the nodes of a “trillium” net. We show that the system is strongly magnetically frustrated: the Néel transition is suppressed well below the characteristic magnetic interaction strength; short-range magnetic order persists far above the Néel temperature; and the magnetic susceptibility exhibits a pseudo-plateau at 1/3-saturation magnetization. A simple model of nearest-neighbor Heisenberg antiferromagnetic and dipolar interactions accounts quantitatively for all observations, including an unusual 2-k magnetic ground state. We show that the relative strength of dipolar interactions is crucial to selecting this particular ground state. Geometric frustration within the classical spin liquid regime gives rise to a large magnetocaloric response at low applied fields that is degraded in powder samples as a consequence of the anisotropy of dipolar interactions.