Pushing T<sub>C</sub> to 27.5 K in a heavy atom radical ferromagnet

Lekin, Kristina; Ogata, Kazuma; Maclean, Adrian M.; Mailman, Aaron; Winter, Stephen M.; Assoud, Abdeljalil; Mito, Masaki; Tse, John S.; Desgreniers, Serge; Hirao, Naohisa; Dube, Paul A.; Oakley, Richard T.

doi:10.1039/c6cc07142b

Cited by 22 publications

(8 citation statements)

References 31 publications

(9 reference statements)

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“…Much of the activity in this field is driven by the desire to better understand the structure and electronic properties of stable radicals and to develop new methods for their preparation. − This research has already led to many practical applications of stable radicals and their polymers as components of polymer and flow batteries, − imaging probes and contrast agents, − active layers in resistive memory devices, − and catalysts for alcohol oxidation …”

Section: Introductionmentioning

confidence: 99%

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

et al. 2018

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The electronic structure of 1,3,5-triphenyl-6oxoverdazyl, a heteroatom-rich stable organic radical, and its diamagnetic 1,3,5-triphenyl-6-oxotetrazane precursor are probed using X-ray absorption near-edge structure (XANES) spectroscopy. The N K-edge XANES spectra of the 6-oxoverdazyl radical contain strong N 1s → π* resonances for each set of equivalent nitrogen atoms. The fact that these resonances are absent from the analogous spectra of the 6-oxotetrazane, whereas the O Kedge and C K-edge XANES spectra of both species are very similar, demonstrates that the unpaired electron of the radical is localized primarily on the N atoms of the 6-oxoverdazyl heterocycle. The O K-edge XANES spectra of both species contain strong O 1s → π* (CO) peaks, but the peak of the radical is red-shifted by 0.5 eV relative to that of the 6-oxotetrazane, which indicates that the CO bond in the radical is part of a larger π-conjugated system. The proposed interpretations of the XANES spectra are aided by density-functional calculations.

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Section: Introductionmentioning

confidence: 99%

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

et al. 2018

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“…For the FMs, Curie temperature (T C ) was increased by applying external pressure, e. g . from T C =10.5 K at normal pressure to T C =27.5 K at 2.4 GPA for a bis(1,2,3‐diselenazole) derivative . Notably, magnetic bistability was found as a consequence of solid‐state interconversion of 1,2,3‐dithiazyl π‐radicals and their N−N σ‐bonded dimers .…”

Section: Applicationsmentioning

confidence: 97%

Synthesis and Applications of 5‐Membered Chalcogen‐Nitrogen π‐Heterocycles with Three Heteroatoms

Ракитин

Zibarev

2018

Asian J Org Chem

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The recent progress in the synthesis of the title heterocycles exemplified by closed-and open-shell 1,2,5chalcogenadiazoles, 1,2,3-dichalcogenazoles and their hybrids (chalcogens: S, Se, and Te), and in actual or potential applications of these compounds in materials science and biomedicine, is discussed. The synthetic importance of the chalcogen exchange, both direct and indirect, is emphasized, as well as the significance of the heavier chalcogen derivatives in the design and synthesis of smart molecular materials.[a] Prof. Scheme 1.Representative examples of 1,2,5-chalcogenadiazoles and 1,2,3dichalcogenazoles including Appel and Herz cations and Herz radicals.

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“…On top of that, radicals are well known for their catalytic activity and biological importance. − Notably, molecular magnetism and catalysis share a library of organic radicals. , It is thus crucial to develop a chemical and theoretical understanding of new organic radicals in order to increase the number of nonmetal paramagnetic building blocks for the synthesis of functional and multifunctional molecular materials . Among many different functionalities of radical-based magnetic compounds, the following seem to be the most popular: electronic conductivity, − long-range magnetic ordering, − valence tautomerism, ,− photomagnetism, ,− luminescence, − and single molecule and single chain magnet behavior (SMM and SCM). ,− …”

Section: Introductionmentioning

confidence: 99%

Influence of the Increasing Number of Organic Radicals on the Structural, Magnetic, and Electrochemical Properties of the Copper(II)–Dioxothiadiazole Family of Complexes

Arczyński

Pinkowicz

2020

Inorg. Chem.

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The preparation, structures, and electrochemical and magnetic properties supported by density functional theory (DFT) calculations of three new copper(II) compounds with [1,2,5]thiadiazolo[3,4- f ][1,10]phenanthroline 1,1-dioxide (td) and its radical anion (td ·– ) are reported: {[Cu II Cl(td)](μ-Cl) 2 [Cu II Cl(td)]} ( 1 ), which incorporates only neutral td ligands; [Cu II Cl(td ·– )(td)]·2MeCN ( 2 ), which comprises one neutral td and one radical td ·– ; and PPN[Cu II Cl(td ·– ) 2 ]·2DMA ( 3 ), where Cu II ions are coordinated by two radical anions td ·– (DMA, dimethylacetamide; PPN + , the bis(triphenylphosphine)iminium cation). All three compounds show interesting paramagnetic behavior with low-temperature features indicating significant antiferromagnetic coupling. The magnetic properties of 1 are dominated by Cu II ···Cu II interactions ( J CuCu ) mediated through the Cl – bridges, while the magnetic properties of 2 and 3 are governed mainly by the td ·– ···td ·– ( J tdtd ) and Cu II –td ·– ( J Cutd ) exchange interactions. The structure of 2 features only two major magnetic coupling pathways enabling the fitting of experimental data with J tdtd = −36.0(5) cm –1 and J Cutd = −12.6(2) cm –1 only. Compound 3 exhibits a complex network of magnetic contacts. Attempt to approximate its magnetic behavior using only a local magnetic contacts model resulted in J tdtd = −5.6(1) cm –1 and two J Cutd constants, −12.4(2) and −22.6(4) cm –1 . The experimental fitting is critically compared with the results of broken symmetry density functional theory (BS DFT) calculations for inter- and intramolecular contacts. More consistent results were obtained with the M06 functional as opposed to popular B3LYP, which encountered problems reproducing some of the experimental intermolecular exchange interactions. Electrochemical measurements of 2 and 3 in MeCN showed three reversible nearly overlapping redox peaks appearing in a narrow potential range of −600 to −100 mV vs Fc/Fc ...

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Pushing T_C to 27.5 K in a heavy atom radical ferromagnet

Cited by 22 publications

References 31 publications

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

Synthesis and Applications of 5‐Membered Chalcogen‐Nitrogen π‐Heterocycles with Three Heteroatoms

Influence of the Increasing Number of Organic Radicals on the Structural, Magnetic, and Electrochemical Properties of the Copper(II)–Dioxothiadiazole Family of Complexes

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Pushing TC to 27.5 K in a heavy atom radical ferromagnet

Cited by 22 publications

References 31 publications

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

Synthesis and Applications of 5‐Membered Chalcogen‐Nitrogen π‐Heterocycles with Three Heteroatoms

Influence of the Increasing Number of Organic Radicals on the Structural, Magnetic, and Electrochemical Properties of the Copper(II)–Dioxothiadiazole Family of Complexes

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Pushing T_C to 27.5 K in a heavy atom radical ferromagnet