In situ tracking and characterisation of scorpionate ligands via11B-NMR spectroscopy

Thomas, Jarrod R.; Sulway, Scott A.

doi:10.1039/d0ra10826j

Cited by 5 publications

(4 citation statements)

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“…Thulium metal was dissolved in HCl before the solution was subjected to vacuum distillation, yielding TmCl 3 ·6H 2 O. 3-(2′-pyridyl)-pyrazole and sodium hydrotris[3-(2′-pyridyl)-pyrazol-1-yl]botare (NaTp 2‑py ) were synthesized via literature procedures and characterized using recently developed in situ spectroscopic techniques . When required, spectroscopic grade solvents were used without further purification, stored under activated 3 Å sieves, and degassed using the standard freeze-pump-thaw technique.…”

Section: Methodsmentioning

confidence: 99%

“…3-(2′-pyridyl)-pyrazole and sodium hydrotris[3-(2′pyridyl)-pyrazol-1-yl]botare (NaTp 2-py ) were synthesized via literature procedures and characterized using recently developed in situ spectroscopic techniques. 48 When required, spectroscopic grade solvents were used without further purification, stored under activated 3 Å sieves, and degassed using the standard freeze-pump-thaw technique. For moisture sensitive synthesis, manipulations were carried out using an argon-filled glovebox and standard Schlenk line technique.…”

Section: ■ Introductionmentioning

confidence: 99%

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Increasing the Symmetry around Lanthanide Ions: The Effect on Single-Ion Magnet Behavior and Electronic Structure

Thomas,

Giansiracusa,

Mole

et al. 2023

Crystal Growth & Design

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Bis-capped lanthanide compounds have dominated the single-ion magnet (SIM) field with little variation in design. Herein, we report the new synthesis of the lanthanide compounds [Ln(Tp 2-py ) 2 ](BPh 4 ) (1-Ln; Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy), which employ the use of the hexadentate hydrotris[3-(2′pyridyl)-pyrazol-1-yl]borate (Tp 2-py ) ligand to encapsulate lanthanide ions in pseudo-icosahedral crystal fields. The extension of the latter lanthanide ions yields the hydrated compounds [Ln(κ 4 -Tp 2-py ) 2 (OH 2 )](BPh 4 ) (2-Ln; Ln = Dy, Y, Ho, Er, Tm, Yb, and Lu) instead due to the decrease in the ionic radii of the lanthanide and steric demand of the ligand. Alternating current magnetometry studies on 1-Ce, 1-Tb, 1-Dy, 2-Dy, and [Dy(Tp 2-py ) 2 Cl] (3) revealed slow magnetic relaxation in applied magnetic fields for all compounds, with 1-Tb revealing an extractable Orbach regime with U eff = 46(2) cm −1 , while the remaining compounds are dominated by Raman relaxation mechanisms. The complexity and size of Tp 2-py likely afford many low energy vibrational modes which would be responsible for an increase in spin-phonon coupling and the observed dominance of Raman relaxation. CASSCF calculations on the compounds showed that the ground state purity is heavily dependent on the lanthanide; however, all easy axes are aligned with the B•••B axis (or pseudo B•••B axis for the case of 3) except for 2-Dy, where the easy axis aligns with the Dy−OH 2 bond. The resonant nature of the tris-(pyrazolyl)borate ligands results in diffusely spread charge distribution, minimizing the influence of the axially located boron atoms, resulting in the lanthanide ion being encapsulated in a "pseudosphere" of negative charge, impacting the overall crystal field splitting. The magnetic behavior and electronic structure of 1-Ln highlight the importance of low energy vibrational modes to mitigate spin-phonon coupling, charge distribution, and geometry of ligands when designing lanthanide-based SIMs.

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Section: Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Increasing the Symmetry around Lanthanide Ions: The Effect on Single-Ion Magnet Behavior and Electronic Structure

Thomas,

Giansiracusa,

Mole

et al. 2023

Crystal Growth & Design

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“…NaTp 2-Fu was synthesized according to literature procedures (Halcrow et al, 1997), with progression of the pyrazolyl substitution tracked by our in-situ methods (Thomas et al, 2021). [Ce(Tp 2-Fu ) 2 ](BPh 4 )•2CH 2 Cl 2 (1-Ce) was prepared by an adapted literature procedure with analogous ligands (Jones et al, 1997;Thomas et al, 2024), i.e.…”

Section: Synthesis and Crystallizationmentioning

confidence: 99%

Borotropic shifting of the hydrotris[3-(2-furyl)pyrazol-1-yl]borate ligand in high-coordinate lanthanide complexes

Thomas,

Sulway

2024

Acta Crystallogr C

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The coordination of hydrotris[3-(2′-furyl)pyrazol-1-yl]borate (Tp2-Fu, C21H16BN6O3) to lanthanide(III) ions is achieved for the first time with the complex [Ln(Tp2-Fu)2](BPh4)·xCH2Cl2 (1-Ln has Ln = Ce and x = 2; 1-Dy has Ln = Dy and x = 1). This was accomplished via both hydrous (Ln = Ce) and anhydrous methods (Ln = Dy). When isolating the dysprosium analogue, the filtrate produced a second crop of crystals which were revealed to be the 1,2-borotropic-shifted product [Dy(κ4-Tp2-Fu)(κ5-Tp2-Fu*)](BPh4) (2) {Tp2-Fu* = hydrobis[3-(2′-furyl)pyrazol-1-yl][5-(2′-furyl)pyrazol-1-yl]borate}. We conclude that the presence of a strong Lewis acid and a sterically crowded coordination environment are contributing factors for the 1,2-borotropic shifting of scorpionate ligands in conjunction with the size of the conical angle with the scorpionate ligand.

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“…S4–S8†). 8 The 19 F spectra showed coupling between the yttrium centre and bound fluoride, which is present in 2-diox and 2-py , with an appropriate coupling constant of 1 J Y–F = 69.4 Hz.…”

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confidence: 97%

Approaching the 1000 K energy barrier in high coordinate lanthanide single-ion magnets: Increasing U_eff in the [Dy(Tp^2-py)F]⁺ moiety with tetrahydrofuran

Thomas,

Giansiracusa,

Sulway

2024

Dalton Trans.

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In situ tracking and characterisation of scorpionate ligands via¹¹B-NMR spectroscopy

Abstract: Using 11B-NMR spectroscopy for the in situ tracking and characterisation of the well known scorpionate ligand class. Five examples are included.

Cited by 5 publications

References 20 publications

Increasing the Symmetry around Lanthanide Ions: The Effect on Single-Ion Magnet Behavior and Electronic Structure

Increasing the Symmetry around Lanthanide Ions: The Effect on Single-Ion Magnet Behavior and Electronic Structure

Borotropic shifting of the hydrotris[3-(2-furyl)pyrazol-1-yl]borate ligand in high-coordinate lanthanide complexes

Approaching the 1000 K energy barrier in high coordinate lanthanide single-ion magnets: Increasing U_eff in the [Dy(Tp^2-py)F]⁺ moiety with tetrahydrofuran

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In situ tracking and characterisation of scorpionate ligands via11B-NMR spectroscopy

Abstract: Using 11B-NMR spectroscopy for the in situ tracking and characterisation of the well known scorpionate ligand class. Five examples are included.

Cited by 5 publications

References 20 publications

Increasing the Symmetry around Lanthanide Ions: The Effect on Single-Ion Magnet Behavior and Electronic Structure

Increasing the Symmetry around Lanthanide Ions: The Effect on Single-Ion Magnet Behavior and Electronic Structure

Borotropic shifting of the hydrotris[3-(2-furyl)pyrazol-1-yl]borate ligand in high-coordinate lanthanide complexes

Approaching the 1000 K energy barrier in high coordinate lanthanide single-ion magnets: Increasing Ueff in the [Dy(Tp2-py)F]+ moiety with tetrahydrofuran

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In situ tracking and characterisation of scorpionate ligands via¹¹B-NMR spectroscopy

Approaching the 1000 K energy barrier in high coordinate lanthanide single-ion magnets: Increasing U_eff in the [Dy(Tp^2-py)F]⁺ moiety with tetrahydrofuran