Modulating the Magnetic Properties of Copper(II)/Nitroxyl Heterospin Complexes by Suppression of the Jahn–Teller Distortion

Greatorex, Sam; Fokin, S. V.; Kulmaczewski, Rafał; Yamada, Mihoko; Céspedes, Oscar; Yoshinari, Nobuto; Konno, Takumi; Sproules, Stephen; Овчаренко, В. И.; Halcrow, Malcolm A.

doi:10.1021/acs.inorgchem.0c01345

Cited by 5 publications

(4 citation statements)

References 45 publications

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“…63,90,92 It also performed well on energy minimizations of a family of Jahn− Teller-active molecular magnets, in another study from our lab. 93 During the analysis, we found that θ is influenced by bowlshaped or S-shaped ligand conformations that are often found in highly distorted [Fe(bpp R ) 2 ] 2+ complexes (Figures 2 and S11). These ligand conformations are influenced by crystal packing effects, which are not described by gas-phase calculations.…”

Section: ■ Results and Discussionmentioning

confidence: 94%

“…The calculations were performed in the gas phase, using the ω-B97X-D GGA functional and 6-311G** basis set . That protocol was chosen because it includes a correction for intramolecular dispersion interactions between nonbonded atoms which can be important for accurate descriptions of Jahn–Teller-active distortions. ,, It also performed well on energy minimizations of a family of Jahn–Teller-active molecular magnets, in another study from our lab …”

Section: Results and Discussionmentioning

confidence: 99%

“… 63 , 90 , 92 It also performed well on energy minimizations of a family of Jahn–Teller-active molecular magnets, in another study from our lab. 93 …”

Section: Results and Discussionmentioning

confidence: 99%

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A Survey of the Angular Distortion Landscape in the Coordination Geometries of High-Spin Iron(II) 2,6-Bis(pyrazolyl)pyridine Complexes

Capel Berdiell,

Michaels,

Munro

et al. 2024

Inorg. Chem.

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Reaction of 2,4,6-trifluoropyridine with sodium 3,4dimethoxybenzenethiolate and 2 equiv of sodium pyrazolate in tetrahydrofuran at room temperature affords 4-(3,4-dimethoxyphenylsulfanyl)-2,6-di(pyrazol-1-yl)pyridine (L), in 30% yield. The iron(II) complexes [FeL 2 ][BF 4 ] 2 (1a) and [FeL 2 ][ClO 4 ] 2 (1b) are high-spin with a highly distorted six-coordinate geometry. This structural deviation from ideal D 2d symmetry is common in highspin [Fe(bpp) 2 ] 2+ (bpp = di{pyrazol-1-yl}pyridine) derivatives, which are important in spin-crossover materials research. The magnitude of the distortion in 1a and 1b is the largest yet discovered for a mononuclear complex. Gas-phase DFT calculations at the ω-B97X-D/6-311G** level of theory identified four minimum or local minimum structural pathways across the distortion landscape, all of which are observed experimentally in different complexes. Small distortions from D 2d symmetry are energetically favorable in complexes with electron-donating ligand substituents, including sulfanyl groups, which also have smaller energy penalties associated with the lowest energy distortion pathway. Natural population analysis showed that these differences reflect greater changes to the Fe−N{pyridyl} σ-bonding as the distortion proceeds, in the presence of more electron-rich pyridyl donors. The results imply that [Fe(bpp) 2 ] 2+ derivatives with electron-donating pyridyl substituents are more likely to undergo cooperative spin transitions in the solid state. The high-spin salt [Fe(bpp) 2 ][CF 3 SO 3 ] 2 , which also has a strong angular distortion, is also briefly described and included in the analysis.

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Section: ■ Results and Discussionmentioning

confidence: 94%

Section: Results and Discussionmentioning

confidence: 99%

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A Survey of the Angular Distortion Landscape in the Coordination Geometries of High-Spin Iron(II) 2,6-Bis(pyrazolyl)pyridine Complexes

Capel Berdiell,

Michaels,

Munro

et al. 2024

Inorg. Chem.

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“…We were able to obtain the HL in an amount not exceeding 0.1 g. However, this amount is enough to reproduce the synthesis of the complex several times and to grow quality single crystals. The latter should be considered as certain luck since, as is known, it is not always possible to grow single crystals of Cu(II) complexes with tridentate nitroxides that are suitable for X-ray crystallography. [CuL 2 ]·0.75CH 2 Cl 2 ·0.5H 2 O was synthesized by the interaction of Cu(OAc) 2 ·H 2 O with HL (Figure ) in a CH 2 Cl 2 –MeOH mixture in the presence of NEt 3 .…”

Section: Resultsmentioning

confidence: 99%

Five-Spin Copper(II) Nitroxide Complex with Apparently Compressed Octahedral Geometry: Design, Synthesis, and Magnetostructural Studies

Veber

Tumanov

Fokin

et al. 2023

Crystal Growth & Design

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Multispin Cu(II)-nitroxide compounds have attracted significant interest in the field of molecular magnetism; however, complexes involving more than three spins in a single molecule have rarely been reported. In this work we describe the synthesis and detailed physicochemical study of the solvated sixcoordinated five-spin complex [CuL 2 ] (L = 2,2′-(1H-pyrrole-2,5diyl)bis(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1oxyl)). This complex features a tridentate meridional coordination of the biradical L, resulting in an exchange-coupled cluster of four radical and one Cu(II) spin. The structural and magnetic properties of [CuL 2 ] have been thoroughly investigated using single-crystal X-ray diffraction (XRD), SQUID magnetometry, electron paramagnetic resonance (EPR), Fourier-transform infrared (FTIR) spectroscopy, and quantum chemical calculations (QCC). An apparently compressed octahedral coordination geometry has been found by XRD, which, however, stems from the superposition of two isomeric structures of elongated octahedral CuN 2 O 4 units. Neither X-ray nor FTIR has revealed any structural transitions in [CuL 2 ] at 8−300 K, whereas the magnetic behavior studied by magnetometry and QCC is governed by temperature-dependent populations of high-spin multiplets. EPR spectroscopy revealed a drastic temperature dependence of the line width in [CuL 2 ], which changes by almost 2 orders of magnitude within 4−300 K. A comparison with EPR and QCC data for close-structure four-and three-spin analogues has revealed an interplay of the temperaturedependent population of high-spin multiplets and intermolecular exchange interactions, which govern the line width in such systems.

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Gadolinium‐Triradical Complex with Ground S = 10 State: Synthesis, Structural Characterization and Magnetic Studies

2021

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Two novel dinuclear lanthanide(III) complexes were prepared with a triradical 2,4,6-tris{p-(N-oxy-N-t-butylamino)phenyl}-1,3,5triazine (L), yielding [{Ln III (hfac) 3 (ethanol)(L)} 2 ] (Ln 2 L 2 , Ln = Gd and La; hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate). Compound Ln 2 L 2 has a cyclic structure in which two Ln ions are bridged by two triradical ligands. The cyclic dimers form quasi-two-dimensional (2D) structures via intermolecular hydrogen bonding and π-π interactions. The La derivative, in which only L shows magnetic behavior, exhibits intraligand ferromagnetic and interligand antiferromagnetic 2 p-2 p couplings. Compound Gd 2 L 2 shows ferromagnetic 4 f-2 p and intraligand 2 p-2 p couplings with a high-spin state of S = 10.

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Modulating the Magnetic Properties of Copper(II)/Nitroxyl Heterospin Complexes by Suppression of the Jahn–Teller Distortion

Cited by 5 publications

References 45 publications

A Survey of the Angular Distortion Landscape in the Coordination Geometries of High-Spin Iron(II) 2,6-Bis(pyrazolyl)pyridine Complexes

A Survey of the Angular Distortion Landscape in the Coordination Geometries of High-Spin Iron(II) 2,6-Bis(pyrazolyl)pyridine Complexes

Five-Spin Copper(II) Nitroxide Complex with Apparently Compressed Octahedral Geometry: Design, Synthesis, and Magnetostructural Studies

Gadolinium‐Triradical Complex with Ground S = 10 State: Synthesis, Structural Characterization and Magnetic Studies

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