The present study introduces a comprehensive exploration in terms of physicochemical characterization and calculations based on density functional theory with Hubbard’s correction (DFT+U) of the whole family of α-Co­(II) hydroxyhalide (F, Cl, Br, I). These samples were synthesized at room temperature by employing a one-pot approach based on the epoxide route. A thorough characterization (powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis/mass spectroscopy, and magnetic and conductivity measurements) corroborated by simulation is presented that analyzes the structural, magnetic, and electronic aspects. Beyond the inherent tendency of intercalated anions to modify the interlayer distance, the halide’s nature has a marked effect on several aspects. Such as the modulation of the CoOh to CoTd ratio, as well as the inherent tendency towards dehydration and irreversible decomposition. Whereas the magnetic behavior is strongly correlated with the CoTd amount reflected in the presence of glassy behavior with high magnetic disorder, the electrical properties depend mainly on the nature of the halide. The computed electronic structures suggest that the CoTd molar fraction exerts a minor effect on the inherent conductivity of the phases. However, the band gap of the solid turns out to be significantly dependent on the nature of the incorporated halide, governed by ligand to metal charge transfer, which minimizes the gap as the anionic radius becomes larger. Conductivity measurements of pressed pellets confirm this trend. To the best of our knowledge, this is the first report on the magnetic and electrical properties of α-Co­(II) hydroxyhalides validated with in silico descriptions, opening the gate for the rational design of layered hydroxylated phases with tunable electrical, optical, and magnetic properties.

In this work we present a systematic computational study of the structural and magnetic properties of a layered family of Co(II) hydroxichlorides, obeying to the general formula Co(OH)Cl (HO) . This solid contains both octahedral and tetrahedral cobalt ions, displaying a complex magnetic order arising from the particular coupling between the two kinds of metallic centers. Here, supercells representing concentrations of 12, 20, and 40% of tetrahedral sites were modeled consistently with the compositions reported experimentally. Our simulations show that the two types of cobalt ions tend to couple antiferromagnetically, giving rise to a net magnetic moment slightly out of the plane of the layers. The band gap reaches its minimum value of 1.4 eV for the most diluted fraction of tetrahedral Co(II) sites, going up to 2.2 eV when the content is 40%. Moreover, our results suggest that the presence of interlayer water stabilizes the material and at the same time strongly modifies the electronic environment of tetrahedral Co(II), leading to a further drop of the band gap. To our knowledge, this is the first theoretical investigation of this material.

Co‐ and Ni‐based layered hydroxides constitute a unique class of two‐dimensional inorganic materials with exceptional chemical diversity, physicochemical properties and outstanding performance as supercapacitors and overall water splitting catalysts. Recently, the occurrence of Co(III) in these phases has been proposed as a key factor that enhance their electrochemical performance. However, the origin of this centers and control over its contents remains as an open question. We employed the Epoxide Route to synthesize a whole set of α‐NiCo layered hydroxides. The PXRD and XAS characterization alert about the occurrence of Co(III) as a consequence of the increment in the Ni content. DFT+U simulation suggest that the shortening of the Co−O distance promotes a structural distortion in the Co environments, resulting in a double degeneration in the octahedral Co 3d orbitals. Hence, a strong modification of the electronic properties leaves the system prone to oxidation, by the appearance of Co localized electronic states on the Fermi level. This work combines a microscopic interpretation supported by a multiscale crystallochemical analysis, regarding the so‐called synergistic redox behavior of Co and Ni, offering fundamental tools for the controllable design of highly efficient electroactive materials. To the best of our knowledge, this is the first computational–experimental investigation of the electronic and structural details of α‐NiCo hydroxides, laying the foundation for the fine tuning of electronic properties in layered hydroxides.

Synchrotron X-ray and neutron diffraction experiments at various temperatures, down to 3 K, along with ab initio calculations, are carried out to elucidate the magnetic order of layered β-cobalt-hydroxide. This combination of techniques allows for the unambiguous assignment of the magnetic structure of this material. Our results confirm that below the Néel temperature high-spin cobalt centers are ferromagnetically coupled within a layer, and antiferromagnetically coupled across layers (magnetic propagation vector k = (0,0,½)), in agreement with the indirect interpretation based on magnetic susceptibility measurements. A paramagnetic/antiferromagnetic transition is observed at around 15 K. Moreover, the thermal expansion behavior along the c-lattice direction, perpendicular to the layers, shows an inflection slightly above this temperature, at around 30 K. The neutron diffraction patterns and the non-collinear DFT+U calculations indicate that the magnetization forms an angle of about 35° with the cobalt planes. In particular, for an isolated ferromagnetic layer, the electronic structure calculations reveal sharp cusps on the potential energy surface when the spins point parallel or perpendicular to the planes, suggesting that the ferromagnetic superexchange mechanism is strongly sensitive to the orientation of the magnetic moment.

A dramatic change in the magnetic behaviour, which solely depends on the parity of the organic linker molecules, has been found in a family of layered CoII hydroxides covalently functionalized with dicarboxylic molecules. These layered hybrid materials have been synthesized at room temperature using a one‐pot procedure through the epoxide route. While hybrids connected by odd alkyl chains exhibit coercive fields (Hc) below ca. 3500 Oe and show spontaneous magnetization at temperatures (TM) below 20 K, hybrids functionalized with even alkyl chains behave as hard magnets with Hc>5500 Oe and display a TM higher than 55 K. This intriguing behaviour was studied by density functional theory with the incorporation of a Hubbard term (DFT+U) calculations, unveiling the structural subtleties underlying this observation. Indeed, the different molecular orientation exhibited by the even/odd alkyl chains, and the orientation of the covalently linked carboxylic groups modify the intensity of the magnetic coupling of both octahedral and tetrahedral in‐plane sublattices, thus strongly affecting the magnetic properties of the hybrid. These findings offer an outstanding level of tuning in the molecular design of hybrid magnetic materials based on layered hydroxides.

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We introduce and discuss a hybrid quantum-mechanics molecular-mechanics (QM-MM) approach for Car-Parrinello DFT simulations with pseudopotentials and planewaves basis, designed for the treatment of periodic systems. In this implementation the MM atoms are considered as additional QM ions having fractional charges of either sign, which provides conceptual and computational simplicity by exploiting the machinery already existing in planewave codes to deal with electrostatics in periodic boundary conditions.With this strategy, both the QM and MM regions are contained in the same supercell, which determines the periodicity for the whole system. Thus, while this method is not meant to compete with non-periodic QM-MM schemes able to handle extremely large but finite MM regions, it is shown that for periodic systems of a few hundred atoms, our approach provides substantial savings in computational times by treating classically a fraction of the particles. The performance and accuracy of the method is assessed through the study of energetic, structural, and dynamical aspects of the water dimer and of the aqueous bulk phase. Finally, the QM-MM scheme is applied to the computation of the vibrational spectra of water layers adsorbed at the TiO 2 anatase (101) solid-liquid interface. This investigation suggests that the inclusion of a second monolayer of H 2 O molecules is sufficient to induce on the first adsorbed layer, a vibrational dynamics similar to that taking place in the presence of an aqueous environment. The present QM-MM scheme appears as a very interesting tool to efficiently perform molecular dynamics simulations of complex condensed matter systems, from solutions to nanoconfined fluids to different kind of interfaces.

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