Disordered magnetic ground state in a quasi-1-Dd4columnar iridate Sr3LiIrO6.

Spin-orbit coupling offers a large variety of novel and extraordinary magnetic and electronic properties in otherwise 'ordinary pool' of heavy ion oxides. Here we present a detailed study on an apparently isolated hexagonal 2Hspin-chaind4iridate Sr3LiIrO6with geometric frustration. Our structural studies reveal Li-Ir chemical order with desired stoichiometry in this compound, while x-ray absorption together with x-ray photoemission spectroscopic characterizations establish pure 5+ valence of Ir. We have established a magnetic ground state with finite Ir5+magnetic moments in this compound, contrary to the anticipated nonmagneticJeff= 0 state, through combined dc susceptibility,7Li nuclear magnetic resonance (NMR), muon spin relaxation (µSR) andab-initioelectronic structure studies. These investigations together with ac magnetic susceptibility and specific heat measurements reveal that despite having noticeable antiferromagnetic correlation among the Ir5+local moments, this system does not magnetically order down to at least 0.05 K, possibly due to geometrical exchange frustration, arising from the comparable nearest- and next-nearest-neighbor interchain Ir-O-O-Ir superexchange interaction strengths with opposite signs. However, the zero-fieldµSR analysis shows emergence of a considerable proportion of spin-freezing on top of a spin-fluctuating dynamic magnetic background down to the lowest measured temperature of 1.7 K, possibly due to some inhomogeneity and/or the much stronger intra-column Ir-Ir magnetic exchange interaction strength relative to the inter-column Ir-Ir ones. The linear temperature dependence of the magnetic specific heat (Cm) in both zero and applied magnetic fields, plus the power-law behavior of the NMR spin-lattice relaxation rate suggest a gapless spinon density of states in this charge gapped disordered magnetic ground state of Sr3LiIrO6.

Probing the Magnetic Ground State of Ba2YIrO6: Impact of Nonmagnetic Dopants and Spin-Orbit Coupling.

Strong spin-orbit coupling (SOC) in iridates has long been predicted to lead to exotic electronic and magnetic ground states. Ba2YIrO6 (BYIO) has attracted particular attention due to the expectation of a Jeff = 0 state for Ir5+ ions under the jj-coupling scheme. However, controversies surround the actual realization of this state, as finite magnetic moments are consistently observed experimentally. We present a multi-physics study of this system by progressively introducing nonmagnetic Sb5+ ions in place of Ir5+ (Ba2YIr​1-ySb​yO​6, BYISO). Despite similar charge and ionic radii, Sb​5+ doping appears highly inhomogeneous, coexisting with a fraction of nearly pure BYIO regions, as confirmed by X-ray diffraction (XRD). This aligns with observations in related compounds. While inhomogeneity creates uncertainty, the doped majority phases offer valuable insights. It is relevant that the inclusion of even small amounts of Sb​5+ (10-20%) leads to a rise in magnetization. This strengthens our previous suggestion that magnetic Ir ions form dynamic singlets in BYIO, resulting in a near-nonmagnetic background. The observed moment enhancement with nonmagnetic doping supports the breakdown of these singlets. Furthermore, the magnetization steadily increases with an increasing Sb​5+ content, contradicting the anticipated approach towards the Jeff = 0 state with increased SOC due to reduced hopping between Ir​5+ ions. This reinforces the presence of individual Ir​5+ moments. Overall, our findings suggest that Ba​2YIrO​6 might not possess sufficiently strong SOC to be solely described within the jj-coupling picture, paving the way for further investigation.

Structural Rearrangement Followed by Entrapment of Subnanometer Building Blocks of Iron Oxyhydroxide in Aqueous Iron Chloride Solutions.

Iron oxyhydroxide, a natural nanophase of iron found in the environment, plays a crucial role in regulating surface and groundwater composition. Recent research proposes that within the nonclassical prenucleation cluster growth model, subnanometer-sized clusters (olation clusters/Fe13 δ-Keggin oxolation clusters) might act as the prenucleation clusters (PNCs) of ferrihydrite or iron oxyhydroxide solid phase. However, these clusters are difficult to characterize as they are only observable momentarily in low-pH, high-Fe concentration solutions before agglomerating into extended solids, keeping the controversy over the true nature of the PNCs alive. In this study, we introduce large quantities of zinc acetate salt (ZA) into iron chloride solutions at the olation-oxolation boundary (3.6 mM Fe3+ at pH ∼2.6). Remarkably, this manipulation is found to alter the structural arrangement of these subnanometer clusters before blocking them in isolation for hours, even at pH 6, where extended iron oxyhydroxide phases typically precipitate. On the other hand, controlled addition of ZA allows partial unblocking, leading to anisotropic agglomeration into cylindrical rod-like structures. Experimental techniques such as synchrotron-based small-angle X-ray scattering, X-ray absorption spectroscopy, high-resolution transmission electron microscopy (TEM), and cryo-TEM, along with density functional theory (DFT) calculations, reveal the nature of the structural rearrangement and the crucial role of Zn2+ ions in cluster stabilization.