Rethinking polyiodides: the role of electron-deficient multicenter bonds.

Despite a bicentennial history, the interest in polyiodides and related systems still flourishes. The chemical puzzle provided by the intricate nature of chemical bonding in these polyanions remains challenging these days. The advent of the halogen bond and the spreading interest in supramolecular interactions of halogen-based systems promoted further recent interest.

Electron-Deficient Multicenter Bonding in Phase Change Materials: A Chance for Reconciliation.

In the last few years, a controversy has been raised regarding the nature of the chemical bonding present in phase change materials (PCMs), many of which are minerals such as galena (PbS), clausthalite (PbSe), and altaite (PbTe). Two opposite bonding models have claimed to be able to explain the extraordinary properties of PCMs in the last decade: the hypervalent (electron-rich multicenter) bonding model and the metavalent (electron-deficient) bonding model. In this context, a third bonding model, the electron-deficient multicenter bonding model, has been recently added.

A re-interpretation of the structure of the silver borate, AgBO, in the light of the extended Zintl-Klemm concept.

The borate AgBO was synthesized at high temperature and at elevated oxygen pressures [Kovalevskiy et al. (2020). Chem.

Rationalization of the crystal structure of eudidymite NaBe[SiO]·HO in light of the extended Zintl-Klemm concept.

The structure of eudidymite is described in light of the extended Zintl-Klemm concept which considers that Na and Be atoms transfer their six valence electrons to the six Si atoms, converting them into Ψ-P which forms a skeleton characteristic of pentels (Group 15 elements) and is similar to that described in the compound (NH)Ge[GeO] when analysed in the same manner. The Si skeleton is formed of bilayers that are connected through BeO groups which are in fact fragments of the β-BeO structure which bridge the two contiguous Si-bilayers by sharing O atoms. In this context, the Be atoms play a dual role, i.

Generalized Stress-Redox Equivalence: A Chemical Link between Pressure and Electronegativity in Inorganic Crystals.

The crystal structure of many inorganic compounds can be understood as a metallic matrix playing the role of a host lattice in which the nonmetallic atomic constituents are located, the Anions in Metallic Matrices (AMM) model stated. The power and utility of this model lie in its capacity to anticipate the actual positions of the guest atoms in inorganic crystals using only the information known from the metal lattice structure. As a pertinent test-bed for the AMM model, we choose a set of common metallic phases along with other nonconventional or more complex structures (face-centered cubic (fcc) and simple cubic Ca, CsCl-type BaSn, hP4-K, and fcc-Na) and perform density functional theory electronic structure calculations.

Unique thermodynamic relationships for ΔH and ΔG for crystalline inorganic salts. I. Predicting the possible existence and synthesis of NaSO and NaSeO. Addendum.

Addendum to Vegas et al. [(2012), Acta Cryst. B68, 511-527].

In-situ laser synthesis of Nd-Al-O coatings: the role of sublattice cations in eutectic formation.

Neodymium aluminate coatings have been prepared in-situ by the laser zone melting (LZM) method, using a CO2 SLAB-type laser emitting at 10.6 µm. Polycrystalline Al2O3 commercial plates have been used as substrates, and coatings were prepared from the corresponding mixtures of powdered neodymium and aluminium oxides as starting materials.

An alternative approach to rationalizing the structures of the cyclotrisilicates: Rb10[Si6O17], Cs8[Si6O16] and Na3Y[Si6O15] by viewing them in light of the extended Zintl-Klemm concept.

The structures of the three dimeric cyclotrisilicate anions [Si6O17](10-), [Si6O16](8-) and [Si6O15](6-) forming part of the compounds Rb10[Si6O17] or Rb14[Si4][Si6O17], Cs8[Si6O16] and Na3Y[Si6O15], respectively, have been described as different ways of condensing the more elemental cyclotrisilicate anions [Si3O9](6-) [Hlukhyy & Fässler (2013). Z. Anorg.

Isoelectronic and isolobal O, CH2, CH3+ and BH3 as electron pairs; similarities between molecular and solid-state chemistry.

A topological analysis of the electron localization function (ELF) of a molecule of hexamethyldisiloxane, (H3C)3-Si-O-Si-(CH3)3, has been carried out, drawing a consistent picture of Si-O-Si bonding both in the linear and angular geometries. The ELF analysis confirms the idea that the O atom, in the linear geometry of (H3C)3-Si-O-Si-(CH3)3, is isolobal with the isoelectronic -CH3(+)- and -BH3- groups, the bonding in the Si-O-Si group being described as a two-electron, three-center (2e, 3c) bond. At the same time, the three oxygen lone pairs mirror the three C-H and B-H bonds, respectively.

Unique thermodynamic relationships for ΔfHo and ΔfGo for crystalline inorganic salts. I. Predicting the possible existence and synthesis of Na2SO2 and Na2SeO2.

The concept that equates oxidation and pressure has been successfully utilized in explaining the structural changes observed in the M(2)S subnets of M(2)SO(x) (x = 3, 4) compounds (M = Na, K) when compared with the structures (room- and high-pressure phases) of their parent M(2)S `alloy' [Martínez-Cruz et al. (1994), J. Solid State Chem.

On the charge transfer between conventional cations: the structures of ternary oxides and chalcogenides of alkali metals.

The structures of ternary oxides and chalcogenides of alkali metals are dissected in light of the extended Zintl-Klemm concept. This model, which has been successfully extended to other compounds different to the Zintl phases, assumes that crystal structures can be better understood if the cation substructures are contemplated as Zintl polyanions. This implies the occurrence of charge transfer between cations, even if they are of the same kind.

High-pressure experimental study on Rb2S: antifluorite to Ni2In-type phase transitions.

The high-pressure behaviour of dirubidium sulfide, Rb(2)S, with antifluorite-type structure under room conditions (space group Fm ̄3m) has been studied up to 8 GPa at room temperature using angle-dispersive X-ray powder diffraction in a diamond-anvil cell (DAC). X-ray measurements have allowed us to completely characterize two phase transitions upon compression: (i) to an anticotunnite-type structure (Pnma) at some pressure between 1 bar and 0.7 GPa, and (ii) to a Ni(2)In-type structure (P6(3)/mmc) at 2.

Towards a generalized vision of oxides: disclosing the role of cations and anions in determining unit-cell dimensions.

Theoretical calculations of the electron-localization function show that, at the volumes of the two CaO phases (rocksalt and CsCl type), the parent Ca structures (fcc: face-centred cubic and sc: simple cubic, respectively) exhibit charge concentration zones which coincide with the positions occupied by the O atoms in their oxides. Similar features, also observed for the pairs Ca/CaF(2) and BaSn/BaSnO(3), are supported by recent high-pressure experiments as well as electron-localization function (ELF) calculations, carried out on elemental K. At very high pressures, the elemental K adopts the hP4 structure, topologically identical to that of the K atoms in high-pressure K(2)S and high-temperature alpha-K(2)SO(4).

Compounds with a 'stuffed' anti-bixbyite-type structure, analysed in terms of the Zintl-Klemm and coordination-defect concepts.

The bixbyite structure (Mn(2)O(3)) (Ia3) is often described as a distorted face-centered cubic (f.c.c.

Pseudoatoms and preferred skeletons in crystals.

The generalization of the Zintl-Klemm concept provides a universal formulation of a crystal structure in terms of universal building skeletons formed by Klemm's pseudoatoms: atoms that behave structurally according to their formal total electron charge. An important difference in this novel view is that charge is considered to be transferred, in the strict Zintl's sense, from the donor cations to the building skeleton as a whole, not specifically to a given atom or ion. Although application is restricted to (IV)-(IV) compounds (group 14 structures), the principle seems to be universal and can be applied to understand, to relate and to predict the structure of complex compounds on the basis of more simple structures, e.

Structural characterization of a new high-pressure phase of GaAsO4.

As in SiO2 which, at high pressures, undergoes the alpha-quartz-->stishovite transition, GaAsO4 transforms into a dirutile structure at 9 GPa and 1173 K. In 2002, a new GaAsO4 polymorph was found by quenching the compound from 6 GPa and 1273 K to ambient conditions. The powder diagram was indexed on the basis of a hexagonal cell (a=8.

Anions in metallic matrices model: application to the aluminium crystal chemistry.

We introduce and discuss an interpretative model of the structure and bonding of inorganic crystals containing metallic elements. The central idea is the conception of the crystal structure of such an inorganic compound as a metallic matrix whose geometric and electronic structures govern the formation and localization of the anions in the lattice. This is the reason for labelling the model anions in metallic matrices (AMM).

The Zintl-Klemm concept applied to cations in oxides. I. The structures of ternary aluminates.

The structures of 94 ternary aluminates are reinterpreted on the basis of the Zintl-Klemm concept and Pearson's generalized octet rule. In aluminates of highly electropositive metals such as alkali, alkaline-earth and rare-earth metals, the Al atoms form three-dimensional skeleta which can be interpreted as if the Al atoms were behaving as Zintl polyanions, adopting the structure of either main-group elements or Zintl polyanions showing the same connectivity. The O atoms are then located close to both the hypothetical two-electron bonds and the lone pairs, giving rise to a tetrahedral coordination.

Structural relationships between cations and alloys; an equivalence between oxidation and pressure.

More than 100 examples are provided of the structural identity between the cation arrays in oxides and their corresponding alloys (binary compounds). Halides and halogenates, sulfides and sulfites and/or sulfates, selenides and selenates, phosphides and phosphates show this behaviour. In some cases, the structure of the cation subarray corresponds to the structure of the alloy at ambient conditions, but in other cases, cations stabilize structures which correspond to those of the high-pressure phases of the alloy, from which an analogy between the insertion of oxygen and the application of pressure can be established.