On the Covalency of Silver–Fluorine Bonds in Compounds of Silver( I ), Silver( II ) and Silver( III )

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.

Section: From Ionic To Covalentsupporting

confidence: 80%

“…In Zoran, I have found a very careful, enthusiastic, and fearless researcher, a trusted collaborator, and ultimately a friend. All successes and failures of our preparative Ag 2+ chemistry reported since 2003 [42] should be credited to our tight collaboration.…”

Section: From Ionic To Covalentmentioning

confidence: 91%

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

2017

J Supercond Nov Magn

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“…For example, the binding energy of the F(1s) electrons for the above-mentioned KAgF 4 is 686.25 eV, which is by nearly 3 eV larger than the corresponding value for AgF [18], and supposedly the largest value ever measured in a fluorine compound. It is important to realize that fluorine is considered to be the most electronegative of chemical elements, and the one which forms predominantly ionic bonds to all metallic elements.…”

Section: Dos MLmentioning

confidence: 99%

“…It turns out that the entire series of such simplified mixing scenarios is nicely exemplified in the X-ray photoelectron spectra of the fluorides of Ag(I), Ag(II) and Ag(III) [18]. Here, X-ray photoelectron spectra trace back mostly the partial contribution from the 4d orbitals of Ag to the total DOS (due to a much larger cross section for interaction of the Ag(4d) rather than F(2p) electrons with X-ray radiation).…”

Section: Dos MLmentioning

confidence: 99%

“…Finally, one can observe an inversion of the roles of 'metal' and 'ligand' for KAgF 4 , a Ag(III) compound, with 60% of the 4d states sitting in the 'ligand band' (!). 3 results of the quantum mechanical density functional theory (DFT) calculations for these systems [11,18]. To the best of our knowledge, KAgF 4 is the first experimentally documented case of 'inversion' of the valence states in a neutral complex in which the ligand is a genuine non-metal (one should note that 'inverse crystal field' systems have been theorized by some in the past [19][20][21]).…”

Section: Dos MLmentioning

confidence: 99%

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Chemistry of silver(II): a cornucopia of peculiarities

Phil. Trans. R. Soc. A.

Mazej

2015

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Silver is the heavier congener of copper in the Periodic Table, but the chemistry of these two elements is very different. While Cu(II) is the most common cationic form of copper, Ag(II) is rare and its compounds exhibit a broad range of peculiar physico-chemical properties. These include, but are not limited to: (i) uncommon oxidizing properties, (ii) unprecedented large mixing of metal and ligand valence orbitals, (iii) strong spin-polarization of neighbouring ligands, (iv) record large magnetic superexchange constants, (v) ease of thermal decomposition of its salts with O-, N- or C-ligands, as well as (vi) robust Jahn–Teller effect which is preserved even at high pressure. These intriguing features of the compounds of Ag(II) will be discussed here together with (vii) a possibility of electromerism (electronic tautomerism) for a certain class of Ag(II) salts.

Prediction of Extremely Strong Antiferromagnetic Superexchange in Silver(II) Fluorides: Challenging the Oxocuprates(II)

Kurzydłowski

2017

Angewandte Chemie

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Strong magnetic coupling between the spins of unpaired electrons is an essential ingredient of many fascinating physical phenomena. Here we report calculations using the hybrid HSE06 functional of magnetic superexchange constants,J ,f or as eries of low-dimensional Cu II and Ag II binary and ternary systems with fluoride and oxide ligands.T he calculations correctly reproduce the sign and sizeo ft he magnetic superexchange constants for prototypical antiferromagnetic (AFM) 1D (J 1D )a nd 2D (J 2D )s ystems,w hile overestimating the absolute values of Jb ya bout 11 %. We find that [AgF] [BF 4 ], aq uasi-1D system with linear infinite [Ag II F + ]chains,ispredicted to exhibit an unprecedented strong AFM superexchange via one atom (F), with J 1D about À300 meV.C ompression of [AgF] [BF 4 ]t o1 0GPa should lead to afurther increase in AFM interactions with J 1D reaching À360 meV at 10 GPa.