Perovskite-like K3TiOF5 Exhibits (3 + 1)-Dimensional Commensurate Structure Induced by Octahedrally Coordinated Potassium Ions.

Elpasolite- and cryolite-type oxyfluorides can be regarded as superstructures of perovskite and exhibit structural diversity. While maintaining a similar structural topology with the prototype structures, changes in the size, electronegativity, and charge of cation and/or anion inevitably lead to structural evolution. Therefore, the nominal one-to-one relation suggested by a doubled formula of perovskite does not guarantee a simple 2-fold superstructure for many cases. Herein, the commensurately modulated perovskite-like K3TiOF5 was refined at 100 K from single-crystal X-ray diffraction data by using a pseudotetragonal subcell with lattice parameters of a = b = 6.066(2) Å and c = 8.628(2) Å. The length of the modulation vector was refined to 0.3a* + 0.1b* + 0.25c*. In the commensurate supercell of K3TiOF5, the B-site Ti4+ and K+ cations in [TiOF5]3- and [KOF5]6- octahedral units were found to be significantly displaced from the average atomic positions refined in the subcell. The displacements of the K+ cations are ±0.76 Å, and those for the Ti4+ cations are approximately ±0.13 Å. One- and two-dimensional solid-state 19F NMR measurements revealed two tightly clustered groups of resonances in a ratio of ca. 4:1, assigned to equatorial and axial fluorine, respectively, consistent with local [TiOF5]3- units. S/TEM results confirmed the average structure. Electronic structure calculations of the idealized I4mm subcell indicate the instability to a modulated structure arises from soft optical modes that is controlled by the octahedrally coordinated B-site potassium ions in the cryolite-type structure.

Predicting the Structure Stability of Layered Heteroanionic Materials Exhibiting Anion Order.

We report a workflow for heteroanionic materials discovery using Pauling's second rule to filter for and predict new candidate materials for synthesis with reduced computational overhead. Using oxyfluoride and oxynitride n = 1 Ruddlesden-Popper compounds as a use-case, we show that a minimization scheme based on the global instability index (GII) efficiently filters up to 50% of highly unstable candidate compositions based on crystal-chemistry grounds. We then validate the minimization scheme using density functional theory (DFT) calculations and find that unexpectedly the GII of stable heteroanionic materials is higher than that of homoanionic oxides owing to significant charge redistribution in compounds containing more than one anionic species. Using this workflow, we predict Sr2AlO3F to be stable and describe our attempts to synthesize a phase-pure material.

Heteroanionic Materials by Design: Progress Toward Targeted Properties.

The burgeoning field of anion engineering in oxide-based compounds aims to tune physical properties by incorporating additional anions of different size, electronegativity, and charge. For example, oxychalcogenides, oxynitrides, oxypnictides, and oxyhalides may display new or enhanced responses not readily predicted from or even absent in the simpler homoanionic (oxide) compounds because of their proximity to the ionocovalent-bonding boundary provided by contrasting polarizabilities of the anions. In addition, multiple anions allow heteroanionic materials to span a more complex atomic structure design palette and interaction space than the homoanionic oxide-only analogs. Here, established atomic and electronic principles for the rational design of properties in heteroanionic materials are contextualized. Also described are synergistic quantum mechanical methods and laboratory experiments guided by these principles to achieve superior properties. Lastly, open challenges in both the synthesis and the understanding and prediction of the electronic, optical, and magnetic properties afforded by anion-engineering principles in heteroanionic materials are reviewed.

Influence of molecular dipole orientations on long-range exponential interaction forces at hydrophobic contacts in aqueous solutions.

Strong and particularly long ranged (>100 nm) interaction forces between apposing hydrophobic lipid monolayers are now well understood in terms of a partial turnover of mobile lipid patches, giving rise to a correlated long-range electrostatic attraction. Here we describe similarly strong long-ranged attractive forces between self-assembled monolayers of carboranethiols, with dipole moments aligned either parallel or perpendicular to the surface, and hydrophobic lipid monolayers deposited on mica. We compare the interaction forces measured at very different length scales using atomic force microscope and surface forces apparatus measurements. Both systems gave a long-ranged exponential attraction with a decay length of 2.0 ± 0.2 nm for dipole alignments perpendicular to the surface. The effect of dipole alignment parallel to the surface is larger than for perpendicular dipoles, likely due to greater lateral correlation of in-plane surface dipoles. The magnitudes and range of the measured interaction forces also depend on the surface area of the probe used: At extended surfaces, dipole alignment parallel to the surface leads to a stronger attraction due to electrostatic correlations of freely rotating surface dipoles and charge patches on the apposing surfaces. In contrast, perpendicular dipoles at extended surfaces, where molecular rotation cannot lead to large dipole correlations, do not depend on the scale of the probe used. Our results may be important to a range of scale-dependent interaction phenomena related to solvent/water structuring on dipolar and hydrophobic surfaces at interfaces.