Rational design of potential spin qubits manipulated by the valence tautomerism mechanism: quantum-chemical modeling of the trinuclear transition metal complexes with bischelate linkers

Старикова, А. А.

doi:10.1039/c7nj01071k

Cited by 10 publications

(1 citation statement)

References 46 publications

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“…24−27 Valence tautomeric molecules have been attached to a metal surface and incorporated into thin films while retaining their switchable properties. 6,28,29 Dinuclear VT complexes are candidates for two-step molecular transitions, and theoretical studies indicate these could be used as a two-qubit quantum gates in quantum information processing 30 or as molecular switches in molecular electronics or spintronics due to their state-dependent conduction properties. 31 The profile of the magnetic transition (Figure 1) is expected to be affected by the electronic communication between the two Co-dioxolene units, which can be controlled for dinuclear bis(dioxolene)-bridged VT systems.…”

Section: ■ Introductionmentioning

confidence: 99%

Understanding the Origin of One- or Two-Step Valence Tautomeric Transitions in Bis(dioxolene)-Bridged Dinuclear Cobalt Complexes

et al. 2020

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Valence tautomerism (VT) involves a reversible stimulated intramolecular electron transfer between a redox-active ligand and redox-active metal. Bis(dioxolene)-bridged dinuclear cobalt compounds provide an avenue toward controlled two-step VT interconversions of the form {Co III -cat-cat-Co III } ⇌ {Co III -cat-SQ-Co II }⇌{Co II -SQ-SQ-Co II } (cat 2− = catecholate, SQ •− = semiquinonate). Design flexibility for dinuclear VT complexes confers an advantage over two-step spin crossover complexes for future applications in devices or materials. The four dinuclear cobalt complexes in this study are bridged by deprotonated 3,3,3′,3′tetramethyl-1,1′-spirobi(indan)-5,5′,6,6′-tetraol (spiroH 4 ) or 3,3,3′,3′-tetramethyl-1,1′-spirobi(indan)-4,4′,7,7′-tetrabromo-5,5′,6,6′-tetraol (Br 4 spiroH 4 ) with Me n tpa ancillary ligands (tpa = tris(2-pyridylmethyl)amine, n = 0−3 corresponds to methylation of the 6-position of the pyridine rings). Complementary structural, magnetic, spectroscopic, and density functional theory (DFT) computational studies reveal different electronic structures and VT behavior for the four cobalt complexes; one-step one-electron partial VT, two-step VT, incomplete VT, and temperature-invariant {Co III -cat-cat-Co III } states are observed. Electrochemistry, DFT calculations, and the study of a mixed-valence {Zn II -cat-SQ-Zn II } analog have allowed elucidation of thermodynamic parameters governing the one-and two-step VT behavior. The VT transition profile is rationalized by (1) the degree of electronic communication within the bis(dioxolene) ligand and (2) the matching of cobalt and dioxolene redox potentials. This work establishes a clear path to the next generation of two-step VT complexes through incorporation of mixed-valence class II and class II-III bis(dioxolene) bridging ligands with sufficiently weak intramolecular coupling.

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Section: ■ Introductionmentioning

confidence: 99%

Understanding the Origin of One- or Two-Step Valence Tautomeric Transitions in Bis(dioxolene)-Bridged Dinuclear Cobalt Complexes

et al. 2020

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Macroscopic Polarization Change of Mononuclear Valence Tautomeric Cobalt Complexes Through the Use of Enantiopure Ligand

Cao

Wenwei

et al. 2022

Chemistry A European J

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The crystallization of a complex having electron transfer properties in a polar space group can induce the polarization switching of a crystal in a specific direction, which is attractive for the development of sensors, memory devices, and capacitors. Unfortunately, the probability of crystallization in a polar space group is usually low. Noticing that enantiopure compounds crystallize in Sohncke space groups, this paper reports a strategy for the molecular design of non‐ferroelectric polarization switching crystals based on the use of intramolecular electron transfer and chirality. In addition, this paper describes the synthesis of a mononuclear valence tautomeric (VT) cobalt complex bearing an enantiopure ligand. The introduction of enantiomer enables the crystallization of the complex in the polar space group (P21). The polarization of the crystals along the b‐axis direction is not canceled out and the VT transition is accompanied by a change in the macroscopic polarization of the polar crystal. Polarization switching via electron transfer is realized at around room temperature.

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Preparation and characterization of magnetic and magnetophotonic materials based on organic free radicals

Tretyakov

2024

Organic Radicals

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Rational design of potential spin qubits manipulated by the valence tautomerism mechanism: quantum-chemical modeling of the trinuclear transition metal complexes with bischelate linkers

Abstract: A new series of transition metal coordination compounds capable of manifesting the properties of logical elements of quantum computers has been computationally designed using the DFT UB3LYP*/6-311++G(d,p) calculations.

Cited by 10 publications

References 46 publications

Understanding the Origin of One- or Two-Step Valence Tautomeric Transitions in Bis(dioxolene)-Bridged Dinuclear Cobalt Complexes

Understanding the Origin of One- or Two-Step Valence Tautomeric Transitions in Bis(dioxolene)-Bridged Dinuclear Cobalt Complexes

Macroscopic Polarization Change of Mononuclear Valence Tautomeric Cobalt Complexes Through the Use of Enantiopure Ligand

Preparation and characterization of magnetic and magnetophotonic materials based on organic free radicals

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