Linear Trimer Molecule Formation by Three-Center–Four-Electron Bonding in a Crystalline Solid RuP

Hirai, Daigorou; Kojima, Kôhei; Katayama, Naoyuki; Kawamura, Masaya; Nishio–Hamane, Daisuke; Hiroi, Zenji

doi:10.1021/jacs.2c06173

Cited by 9 publications

(4 citation statements)

References 57 publications

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“…This results in triplets of dimer-bound hexamers. We recently became aware of a report of the ground state structure of RuP, confirming the P2 1 /c symmetry and linear Ru trimerization involving orbital molecules proposed to be associated with four electron/three center bonding [72]. This is consistent with the low-temperature local structure retrieved from the 1D-PDF analysis.…”

Section: B Implications For Electronic Propertiessupporting

confidence: 79%

Fluctuating Ru trimer precursor to a two-stage electronic transition in RuP

et al. 2022

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Superconductivity in binary ruthenium pnictides occurs proximal to and upon suppression of a nonmagnetic ground state, preceded by a pseudogap phase associated with Fermi surface instability, and its critical temperature, T c , is maximized around the pseudogap quantum critical point. By analogy with isoelectronic iron-based counterparts, antiferromagnetic fluctuations became "usual suspects" as putative mediators of superconducting pairing. Here we report on a high-temperature local symmetry breaking in RuP, the nonsuperconducting parent of the maximum-T c branch of these novel superconductors, revealed by combined nanostructure-sensitive powder and single-crystal x-ray total scattering analyses. Large local distortions of Ru chains associated with orbital-charge trimerization, further assembled into hexamers, exist above the two-stage electronic transition in RuP. In the pseudogap regime the precursors order with distortions retaining their strength, whereas they acquire spin-singlet characteristics which dramatically enhances the distortion as the nonmagnetic ground state establishes. The precursors enable the nonmagnetic ground state and presumed complex oligomerization, and the relevance of pseudogap fluctuations for superconductivity emerges as a distinct prospect. As a transition metal system in which partial d-manifold filling combined with high crystal symmetry promotes electronic instabilities, this represents a further example of local electronic precursors underpinning the macroscopic collective behavior of quantum materials.

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Section: B Implications For Electronic Propertiessupporting

confidence: 79%

Fluctuating Ru trimer precursor to a two-stage electronic transition in RuP

et al. 2022

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“…However, we do not rule out a lower symmetry average structure that could accommodate either dimers or some larger n-unit nonmagnetic cluster arrangement, such as the octamer ground state in CuIr 2 S 4 72 or trimers in RuP. 92 In theory, one would expect λ-RhO 2 and LiRh 2 O 4 to display behavior closer to CuIr 2 S 4 than to MgTi 2 O 4 and LiV 2 O 4 , owing to the general similarity of Rh/Ir chemistry and the comparatively strong SOC in Rh versus Ti/V. However, in both LiRh 2 O 4 and λ-RhO 2 , SOC appears to play a smaller role in relation to the Jahn−Teller instability of the low-energy Rh 4+ t 2g orbital manifold.…”

Section: ■ Results and Discussionmentioning

confidence: 86%

“…It appears as though dimerization is strongly favored at the local scale through local bonding interactions. However, we do not rule out a lower symmetry average structure that could accommodate either dimers or some larger n -unit nonmagnetic cluster arrangement, such as the octamer ground state in CuIr 2 S 4 or trimers in RuP …”

Section: Resultsmentioning

confidence: 87%

Soft-Chemical Synthesis, Structure Evolution, and Insulator-to-Metal Transition in Pyrochlore-like λ-RhO₂

Chamorro,

Zuo,

Bassey

et al. 2024

Chem. Mater.

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λ-RhO 2 , a prototype 4d transition metal oxide, has been prepared by the oxidative delithiation of spinel LiRh 2 O 4 using ceric ammonium nitrate. Average-structure studies of this RhO 2 polytype, including synchrotron powder X-ray diffraction and electron diffraction, indicate the room-temperature structure to be tetragonal, in space group I4 1 /amd, with a first-order structural transition to cubic Fd3̅ m at T = 345 K on warming. Synchrotron X-ray pair distribution function analysis and 7 Li solid-state nuclear magnetic resonance measurements suggest that the room-temperature structure displays local Rh−Rh bonding. The formation of these local dimers appears to be associated with a metal-to-insulator transition with a nonmagnetic ground state, as also supported by density functional theory-based electronic structure calculations. This contribution demonstrates the power of soft chemistry to kinetically stabilize a simple binary oxide compound.

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“…The situation is different in molecules, even inside solids, where such symmetry restrictions must not be obeyed. One example is the recent finding of ERMBs in the low-temperature monoclinic phase of crystalline RuP, where linear 3c-4e bonds have been found in molecular Ru-Ru-Ru units (the central and external Ru atoms of the trimer occupy different 4e Wyckoff sites) along zigzag-like ladders [188]. Therefore, we consider that ERMBs with equal bond distances are not possible in linear molecules of more than three atoms inside crystalline solids, thus MMBs in solids cannot be equivalent to ERMBs.…”

Section: Nature Of Metavalent Multicenter Bondingmentioning

confidence: 99%

Metavalent multicenter bonding in pnictogens and chalcogens: nature and mechanism of formation

Osman,

Otero-de-la-Roza,

Rodríguez-Hernández

et al. 2023

Preprint

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Due to the exceptional property portfolio and technological applications of phase change materials, mostly chalcogens related to IV-VI and V2-VI3 families, which are in turn related to pnictogens (group V or 15) and chalcogens (group VI or 16), the nature of the unconventional chemical bonding in these materials has been debated for almost 70 years. This unconventional bond, which has been quoted in the literature as resonant, hypervalent, electron-rich multicenter, three-center-four-electron (3c-4e), and metavalent, is believed to be responsible for the exceptional properties of phase change materials. In the last decade, two bonding models, the metavalent and the electron-rich multicenter models, have competed to explain the nature of this unconventional bond, which we have here renamed as metavalent multicenter bond (MMB) for the sake of clarity. In this comprehensive work, we address the nature of MMB and propose that MMB is an electron-deficient multicenter bond (EDMB), related to the threecenter-two-electron (3c-2e) bond. For that purpose, we explore the pressure-induced mechanism of MMB formation in the some of the simplest possible systems, pnictogens (As, Sb, Bi) and chalcogens (Se, Te, Po), with density-functional theory calculations. In the way, we find that polonium is the only element among chalcogens and pnictogens with crystalline α and β structures already exhibiting MMBs at RP. We find that the mechanism of MMB formation in pnictogens (chalcogens) is comprised of three (two) stages, is similar to that of the EDMB formation in B2H6, in some Zintl phases, intermetallics, and cluster compounds, and in atomic/polymeric nitrogen and hydrogen at high pressures. On the other hand, the mechanism of EDMB formation is completely different from that of the 3c-4e bond formation in molecules. Finally, we propose the simplest geometries of EDMBs that can be found in solids along one, two, and three dimensions and comment on the validity of the doublet/octet rules in the hypercoordinated multicenter units with EDMBs.

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Linear Trimer Molecule Formation by Three-Center–Four-Electron Bonding in a Crystalline Solid RuP

Cited by 9 publications

References 57 publications

Fluctuating Ru trimer precursor to a two-stage electronic transition in RuP

Fluctuating Ru trimer precursor to a two-stage electronic transition in RuP

Soft-Chemical Synthesis, Structure Evolution, and Insulator-to-Metal Transition in Pyrochlore-like λ-RhO₂

Metavalent multicenter bonding in pnictogens and chalcogens: nature and mechanism of formation

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Linear Trimer Molecule Formation by Three-Center–Four-Electron Bonding in a Crystalline Solid RuP

Cited by 9 publications

References 57 publications

Fluctuating Ru trimer precursor to a two-stage electronic transition in RuP

Fluctuating Ru trimer precursor to a two-stage electronic transition in RuP

Soft-Chemical Synthesis, Structure Evolution, and Insulator-to-Metal Transition in Pyrochlore-like λ-RhO2

Metavalent multicenter bonding in pnictogens and chalcogens: nature and mechanism of formation

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Product

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About

Soft-Chemical Synthesis, Structure Evolution, and Insulator-to-Metal Transition in Pyrochlore-like λ-RhO₂