The structures of inorganic crystals: A rational explanation from the chemical pressure approach and the anions in metallic matrices model

Recio, J. M.; Lobato, Álvaro; Osman, Hussien H.; Salvadó, Miguel A.; Vegas, Α.

doi:10.1016/b978-0-12-823144-9.00097-2

Cited by 2 publications

(3 citation statements)

References 72 publications

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“…The idea of metallic reminiscence is not new and has been also exploited to rationalize the structures of inorganic crystals ,− and electrides, − to discuss whether heavy alkali suboxides are electrides, metals, or alkalides, and also used to detect the most probable sites associated with subvalence in new honeycomb layered Ag 2 M 2 TeO 6 (M: Ni, Co, Mg, etc.) silver materials. , In the latter example, subvalence is not explicitly revealed by the chemical composition but is a result of silver-deficient regions compensated by Ag 6 M 2 TeO 6 domains containing quasi-independent metallic subvalent silver layers.…”

Section: Introductionmentioning

confidence: 99%

“…The idea of metallic reminiscence is not new and has been also exploited to rationalize the structures of inorganic crystals 11 , 17 − 19 and electrides, 20 − 22 to discuss whether heavy alkali suboxides are electrides, metals, or alkalides, 23 and also used to detect the most probable sites associated with subvalence in new honeycomb layered Ag 2 M 2 TeO 6 (M: Ni, Co, Mg, etc.) silver materials.…”

Section: Introductionmentioning

confidence: 99%

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Where are the Excess Electrons in Subvalent Compounds? The Case of Ag₇Pt₂O₇

Izquierdo-Ruiz,

Salvadó,

Lobato

et al. 2024

Inorg. Chem.

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Subvalent compounds raise the question of where those valence electrons not belonging to chemical bonds are. In the limiting case of Ag 7 Pt 2 O 7 , there is just one-electron excess in the chemical formula requiring the presence of Ag atoms with oxidation states below +1, assuming conventional Pt 4+ and O 2− ions. Such a situation challenges the understanding of the semiconducting and diamagnetic behavior observed in this oxide. Previous explanations that localize pairwise the electron excess in tetrahedral Ag 4 interstices do not suffice in this case, since there are six silver tetrahedral voids and only an excess of nine electrons in the unit cell. Here, we provide an alternative explanation for the subvalent nature of this compound by combining interatomic distances, electron density-based descriptors, and orbital energetic analysis criteria. As a result, Ag atoms that do not participate in their valence electron are revealed. We identify excess electrons located in isolated subvalent silver clusters with electron-deficient multicenter bonds resembling pieces of metallic bonding in fcc-Ag and Ag 7 Pt 2 alloy. Our analysis of the electronic band structure also supports the multicenter bonding picture. This combined approach from the real and reciprocal spaces reconciles existing discrepancies and is key to understanding the new chemistry of silver subvalent compounds.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Where are the Excess Electrons in Subvalent Compounds? The Case of Ag₇Pt₂O₇

Izquierdo-Ruiz,

Salvadó,

Lobato

et al. 2024

Inorg. Chem.

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“…Chemical pressure is an efficient tool to tune properties and create functional materials. − The intentional introduction or substitution of chemical elements into a material is a fundamental process to modify its intrinsic structure and properties while changing its composition. − Usually, chemical pressure is mainly associated with structural effects provoked by the different sizes of the doping agents with respect to the host structure. These strains can recreate the response of the material under stress conditions facilitating the equivalence between physical or mechanical pressure and chemical pressure.…”

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confidence: 99%

A Chemical-Pressure-Induced Phase Transition Controlled by Lone Electron Pair Activity

Gomes

Gouveia

Gracia

et al. 2022

J. Phys. Chem. Lett.

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The chemical pressure approach offers a new paradigm for property control in functional materials. In this work, we disclose a correlation between the β → α pressure-induced phase transition in SnMoO4 and the substitution process of Mo6+ by W6+ in SnMo1–x W x O4 solid solutions (x = 0–1). Special attention is paid to discriminating the role of the lone pair Sn2+ cation from the structural distortive effect along the Mo/W substitution process, which is crucial to disentangle the driven force of the transition phase. Furthermore, the reverse α → β transition observed at high temperature in SnWO4 is rationalized on the same basis as a negative pressure effect associated with a decreasing of W6+ percentage in the solid solution. This work opens a versatile chemical approach in which the types of interactions along the formation of solid solutions are clearly differentiated and can also be used to tune their properties, providing opportunities for the development of new materials.

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The structures of inorganic crystals: A rational explanation from the chemical pressure approach and the anions in metallic matrices model

Cited by 2 publications

References 72 publications

Where are the Excess Electrons in Subvalent Compounds? The Case of Ag₇Pt₂O₇

Where are the Excess Electrons in Subvalent Compounds? The Case of Ag₇Pt₂O₇

A Chemical-Pressure-Induced Phase Transition Controlled by Lone Electron Pair Activity

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The structures of inorganic crystals: A rational explanation from the chemical pressure approach and the anions in metallic matrices model

Cited by 2 publications

References 72 publications

Where are the Excess Electrons in Subvalent Compounds? The Case of Ag7Pt2O7

Where are the Excess Electrons in Subvalent Compounds? The Case of Ag7Pt2O7

A Chemical-Pressure-Induced Phase Transition Controlled by Lone Electron Pair Activity

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Where are the Excess Electrons in Subvalent Compounds? The Case of Ag₇Pt₂O₇

Where are the Excess Electrons in Subvalent Compounds? The Case of Ag₇Pt₂O₇