Real and Hypothetical Intermediate-Valence AgII/AgIII and AgII/AgI Fluoride Systems as Potential Superconductors

Grochala, Wojciech; Hoffmann, Roald

doi:10.1002/1521-3773(20010803)40:15<2742::aid-anie2742>3.0.co;2-x

Cited by 154 publications

(173 citation statements)

References 386 publications

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“…We note here that while studying the optical spectra of many transition metal compounds, Jørgensen has introduced the concept of optical electronegativity (OEN) to explain the energies of CT bands [32]. Our analysis has shown that, remarkably, divalent silver fluorides and divalent copper oxides exhibit very similar difference of OEN between metal and nonmetal sites of 0.8-1.1 [16]. Thus, their CT gaps should be similar and rather narrow.…”

Section: From Colorless To Blacksupporting

confidence: 91%

“…This anomalous feature renders Ag 2+ a very strong oxidizer in chemistry, one of the very few known [23]. Doing a careful literature search on Ag 2+ systems, I have learned that they may form 0D, 1D, or even 2D lattices (thus, Ag-F-Ag bridges are found [16]) and that the second ionization potential of silver (which partly governs the formation of its compounds) approaches 21.5 eV in the gas phase, and it is by far the largest value among all metals (except, obviously, the alkali metals, which do not adopt divalent state in chemical compounds). Obviously, this value is reduced in solid state systems or in solution due to the presence of electron pairs from the solvent or ligands (down probably to 9.0-12.5 eV, depending on a system, but these are huge values anyway).…”

Section: From Smaller To Larger Electron Binding Energiesmentioning

confidence: 99%

“…Guided by the expected similarity (Fig. 2), we have performed simple spin unpolarized density of states calculations for model Ag 2+ /F systems, and compared the results to those for Cu 2+ /O systems [16]. Numerous striking similarities were found including substantial hybridization of the d/p states and large dispersion (regions of low DOS) for the highest e g bands for systems showing short Ag-F-Ag links.…”

Section: From Copper Oxides To Silver Fluoridesmentioning

confidence: 99%

“…All those similarities, taken together, helped us to build the claim that high-T C superconductivity could be observed in doped fluorides of Ag 2+ [16]. While this paper was in preparation, we had numerous thought exchanges with the late Müller, Bartlett, andŽemva (they are specifically quoted in [16]).…”

Section: From Copper Oxides To Silver Fluoridesmentioning

confidence: 99%

“…The chemistry of Ag 2+ derivatives has been beautifully developed in the post-war period 1950-2000, mostly by three groups: Hoppe and later Müller in Giessen, Bartlett and coworkers at Berkeley, andŽemva in Slovenia, the latter two in close collaboration (details are outlined in comprehensive review [16]). About 100 distinct chemical compounds evolved from this research, a great majority of them hosting only F atoms in the vicinity of a voracious Ag 2+ center.…”

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confidence: 99%

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Silverland: the Realm of Compounds of Divalent Silver—and Why They are Interesting

Grochala

2017

J Supercond Nov Magn

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In this personal account, the author takes readers on the journey to "Silverland," i.e., the emerging field of electronic and magnetic materials based on divalent silver (Ag 2+ ). He blends historical background with the reasons which led him to become involved in this research, as well as to proposing (with Roald Hoffmann, 2001) that high-T C superconductivity might ultimately be observed in doped Ag 2+ fluorides. More recent experimental and theoretical findings related to novel compounds, and their electronic and magnetic structure, are presented.

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Section: From Colorless To Blacksupporting

confidence: 91%

Section: From Smaller To Larger Electron Binding Energiesmentioning

confidence: 99%

Section: From Copper Oxides To Silver Fluoridesmentioning

confidence: 99%

Section: From Copper Oxides To Silver Fluoridesmentioning

confidence: 99%

mentioning

confidence: 99%

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Silverland: the Realm of Compounds of Divalent Silver—and Why They are Interesting

Grochala

2017

J Supercond Nov Magn

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Fluorides: Solid‐State Chemistry

Massa

2005

Encyclopedia of Inorganic Chemistry

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Inorganic solid fluorides and fluorometalates play a unique role in inorganic chemistry. The preparation, mostly using aqueous or anhydrous HF or even elemental F 2 , requires special conditions: no glass or silicate containing vessels can be used. Their structural chemistry is governed by the outsider role of the fluoride anion. It is the smallest and least polarizable anion and its mainly ionic compounds follow the rules of hard spheres packing better than any other class of substances. Nearly all metal ions except those with the largest ionic radii form fluoride structures with octahedral [M n + F 6 ] (6− n )– units. If the metal:fluorine ratio is less than 6, these octahedra share common vertices or, in rare cases, edges or even faces to account for electroneutrality, the more the lower the oxidation state of the metal. In this way, a variety of 1D chain, 2D net, and 3D framework structures is formed that can be classified into a few large structure families. In binary fluorides, for example, VF 5 has an octahedral cis‐chain structure, VF 4 a layer structure based on a square net of corner‐connected octahedra, VF 3 has a ReO 3 ‐related 3D structure with all corners of octahedra connected, and VF 2 has the rutile‐type structure with partial edge‐sharing of octahedra. In ternary or quaternary compounds, for example, alkali or alkaline earth fluorometalates, the same principles are valid for the anionic substructure while the counter cations fill interstices and stabilize at the same time the structure. The main structure families are grouped according to the basic principles of octahedral nets. These are the ReO 3 ‐related trifluorides, the fluoride perovskites AMF 3 , their relatives elpasolites A 2 A′MF 6 , and cryolites A 3 MF 6 , as well as some layer structures with square nets. A second large family is based on mixed octahedral nets including triple units: it includes for example, the pyrochlores, the weberites, the hexagonal and tetragonal tungsten bronze structures, and some derivable layer structures. Recent developments deal with ‘tailoring’ of low‐dimensional or framework structures using ‘soft‐chemistry’ methods. The relatively simple structural chemistry of fluorides invoked their use as model systems, for instance, for the investigation of electronic effects like Jahn–Teller ordering, or for magnetic investigations. Besides the cryolite Na 3 AlF 6 used in Al production, some fluorides are of technical interest owing to their special optical properties (e.g. laser optics, fluoride glasses), their ability for fluoride ion conductivity, or their role as catalysts for fluorinations or halogene exchange in organic systems.

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X-Ray Crystal Structures of Hexa-oxotellurate Complexes of Ruthenium(VI) and Silver(III): Na6[RuO2{TeO4(OH)2}2]·16H2O and Na5[Ag{TeO4(OH)2}2]·16H2O

Hector¹,

Hill²,

Levason³

et al. 2002

Z. anorg. allg. Chem.

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Real and Hypothetical Intermediate-Valence AgII/AgIII and AgII/AgI Fluoride Systems as Potential Superconductors

Cited by 154 publications

References 386 publications

Silverland: the Realm of Compounds of Divalent Silver—and Why They are Interesting

Silverland: the Realm of Compounds of Divalent Silver—and Why They are Interesting

Fluorides: Solid‐State Chemistry

X-Ray Crystal Structures of Hexa-oxotellurate Complexes of Ruthenium(VI) and Silver(III): Na6[RuO2{TeO4(OH)2}2]·16H2O and Na5[Ag{TeO4(OH)2}2]·16H2O

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