Ferroelectric and Spin Crossover Behavior in a Cobalt(II) Compound Induced by Polar‐Ligand‐Substituent Motion

Akiyoshi, Ryohei; Komatsumaru, Yuki; Donoshita, Masaki; Dekura, Shun; Yoshida, Yukihiro; Kitagawa, Hiroshi; Kitagawa, Yasutaka; Lindoy, Leonard F.; Hayami, Shinya

doi:10.1002/ange.202015322

Cited by 6 publications

(5 citation statements)

References 51 publications

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“…More recently, the group of Hayami investigated a Co II complex bearing a terpyridine unit with a ((3‐fluorophenyl)ethynyl) substituent in the para position of the central pyridine ring (FPh‐terpy), that exhibit SCO behavior that is dependent on the degree of motion of the fluorophenyl ring. A ferroelectric hysteresis loop and spontaneous polarization is induced due to an electrically reversible dipole moment which results from the motion [26] …”

Section: Introductionmentioning

confidence: 99%

Electrochemistry and Spin‐Crossover Behavior of Fluorinated Terpyridine‐Based Co(II) and Fe(II) Complexes

et al. 2023

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Due to their ability to form stable molecular complexes that have tailor‐made properties, terpyridine ligands are of great interest in chemistry and material science. In this regard, we prepared two terpyridine ligands with two different fluorinated phenyl rings on the backbone. The corresponding CoII and FeII complexes were synthesized and characterized by single‐crystal X‐ray structural analysis, electrochemistry and temperature‐dependent SQUID magnetometry. Single crystal X‐ray diffraction analyses at 100 K of these complexes revealed Co−N and Fe−N bond lengths that are typical of low spin CoII and FeII centers. The metal centers are coordinated in an octahedral fashion and the fluorinated phenyl rings on the backbone are twisted out of the plane of the terpyridine unit. The complexes were investigated with cyclic voltammetry and UV/Vis‐NIR spectroelectrochemistry. All complexes show a reversible oxidation and several reduction processes. Temperature dependent SQUID magnetometry revealed a gradual thermal SCO behavior in two of the complexes, while EPR spectroscopy provided further insights on the electronic structure of the metal complexes, as well as site of reduction.

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Section: Introductionmentioning

confidence: 99%

Electrochemistry and Spin‐Crossover Behavior of Fluorinated Terpyridine‐Based Co(II) and Fe(II) Complexes

et al. 2023

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“…Modern experimental studies on SCO processes, whether they are induced by pressure or not, are usually accompanied by simulations. [214][215][216] However, conducting such simulations in a meaningful and reliable way is far from trivial, owing to the intricate interplay between temperature and pressure in the SCO process. The T 1=2 temperature, that is, the temperature at which the HS and the LS state are equally populated, is a key observable, which necessitates some statistical analysis.…”

Section: Spin Crossover Processesmentioning

confidence: 99%

“…Modern experimental studies on SCO processes, whether they are induced by pressure or not, are usually accompanied by simulations 214–216 . However, conducting such simulations in a meaningful and reliable way is far from trivial, owing to the intricate interplay between temperature and pressure in the SCO process.…”

Section: Applicationsmentioning

confidence: 99%

Computational high‐pressure chemistry: Ab initio simulations of atoms, molecules, and extended materials in the gigapascal regime

Zeller,

Hsieh,

Dononelli

et al. 2024

WIREs Comput Mol Sci

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The field of liquid‐phase and solid‐state high‐pressure chemistry has exploded since the advent of the diamond anvil cell, an experimental technique that allows the application of pressures up to several hundred gigapascals. To complement high‐pressure experiments, a large number of computational tools have been developed. These techniques enable the simulation of chemical systems, their sizes ranging from single atoms to infinitely large crystals, under high pressure, and the calculation of the resulting structural, electronic, and spectroscopic changes. At the most fundamental level, computational methods using carefully tailored wall potentials allow the analytical calculation of energies and electronic properties of compressed atoms. Molecules and molecular clusters can be compressed either via mechanochemical approaches or via more sophisticated computational protocols using implicit or explicit solvation approaches, typically in combination with density functional theory, thus allowing the simulation of pressure‐induced chemical reactions. Crystals and other periodic systems can be routinely simulated under pressure as well, both statically and dynamically, to predict the changes of crystallographic data under pressure and high‐pressure crystal structure transitions. In this review, the theoretical foundations of the available computational tools for simulating high‐pressure chemistry are introduced and example applications demonstrating the strengths and weaknesses of each approach are discussed.This article is categorized under: Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Ab Initio Electronic Structure Methods Software > Simulation Methods

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“…Modern experimental studies on SCO processes, whether they are induced by pressure or not, are usually accompanied by simulations. [205][206][207] However, conducting such simulations in a meaningful and reliable way is far from trivial, owing to the intricate interplay between temperature and pressure in the SCO process. The T 1/2 temperature, i.e., the temperature at which the HS and the LS state are equally populated, is a key observable, which necessitates some statistical analysis.…”

Section: Spin Crossover Processesmentioning

confidence: 99%

Computational High-Pressure Chemistry: Ab Initio Simulations of Atoms, Molecules and Extended Materials in the Gigapascal Regime

Zeller,

Hsieh,

Dononelli

et al. 2023

Preprint

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The field of liquid-phase and solid-state high-pressure chemistry has exploded since the advent of the diamond anvil cell, an experimental technique that allows the application of pressures up to several hundred gigapascal. To complement high-pressure experiments, a large number of computational tools have been developed. These techniques enable the simulation of chemical systems, their sizes ranging from single atoms to infinitely large crystals, under high pressure and the calculation of the resulting structural, electronic and spectroscopic changes. At the most fundamental level, computational methods using carefully tailored wall potentials allow the analytical calculation of energies and electronic properties of compressed atoms. Molecules and molecular clusters can be compressed either via mechanochemical approaches or via more sophisticated computational protocols using implicit or explicit solvation approaches, typically in combination with Density Functional Theory, thus allowing the simulation of pressure-induced chemical reactions. Crystals and other periodic systems can be routinely simulated under pressure as well, both in a static and in a dynamic manner, to predict the changes of crystallographic data under pressure and high-pressure crystal structure transitions. In this review, the theoretical foundations of the available computational tools for simulating high-pressure chemistry are introduced and example applications demonstrating the strengths and weaknesses of each approach are discussed.

show abstract

Ferroelectric and Spin Crossover Behavior in a Cobalt(II) Compound Induced by Polar‐Ligand‐Substituent Motion

Cited by 6 publications

References 51 publications

Electrochemistry and Spin‐Crossover Behavior of Fluorinated Terpyridine‐Based Co(II) and Fe(II) Complexes

Electrochemistry and Spin‐Crossover Behavior of Fluorinated Terpyridine‐Based Co(II) and Fe(II) Complexes

Computational high‐pressure chemistry: Ab initio simulations of atoms, molecules, and extended materials in the gigapascal regime

Computational High-Pressure Chemistry: Ab Initio Simulations of Atoms, Molecules and Extended Materials in the Gigapascal Regime

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