Hexahalorhenate(IV) salts of metal oxazolidine nitroxides

Anders H. Pedersen, Blaise L. Geoghegan, Gary S. Nichol, David W. Lupton, Keith S. Murray, José Martínez-Lillo, Ian A. Gass, Euan K. Brechin

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Eight coordination compounds of formulae [FeII(L•)2][ReIVCl6] (1a), [FeII(L•)2][ReIVBr6] (1b), [CoII(L•)2][ReIVCl6]·CH3CN (2a), [CoII(L•)2][ReIVBr6] (2b), [NiII(L•)(CH3CN)3][ReIVCl6]·CH3CN (3a), [NiII(L•)(CH3CN)3][ReIVBr6]·3CH3CN (3b), [CuII(L•)2][ReIVCl6] (4a)and [CuII(L•)2][ReIVBr6] (4b), where L• is the aminoxyl radical chelating ligand, 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N- oxide, have been synthesised. Structural and magnetic studies reveal metal-radical intramolecular antiferromagnetic interactions in the [MII(L•)2]2+ cations in the iron, cobalt and copper based compounds (1a, 1b, 2a, 2b, 4a and 4b) with the central metal ion low-spin in the case of Fe (1a and 1b) and a gradual, cobalt based, spin-crossover transition present in 2a and 2b. The nickel based compounds, 3a and 3b, were analysed in the dried form (3a(dried) and 3b(dried)) and directly in acetonitrile (3a(solvated) and 3b(solvated)). Microanalysis and IR spectroscopy on 3a(dried) and 3b(dried) suggests the dried samples are best formulated as [NiII(L•)(H2O)3][ReIVX6], where X = Cl (3a(dried)) and Br (3b(dried)). All forms for 3a and 3b exhibit cationic metal-radical ferromagnetic interactions resulting in S = 3/2 ground states. In addition, 3a(dried) exhibits spin-canting behaviour with an ordering temperature of 2.7 K, an open hysteresis loop with a coercive field Hc, = 580 Oe, and a remanent magnetisation Mr = 0.21 μB, resulting in a canting angle of ~1.8°. In contrast 3b(dried) shows no spin-canting behaviour; a maximum in χM vs. T at T = 3 K suggesting long-range antiferromagnetic order. 3a(solvated) and 3b(solvated) show no indication of long-range magnetic ordering, unlike 4a and 4b where anomalies are evident in the low-temperature magnetic susceptibility measurements.
Original languageEnglish
Pages (from-to)5250-5259
Number of pages10
JournalDalton Transactions
Volume46
DOIs
Publication statusPublished - 20 Mar 2017

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Cobalt
Magnetization
Salts
Metals
Microanalysis
Hysteresis loops
Chelation
Nickel
Magnetic susceptibility
Oxides
Ground state
Metal ions
Cations
Copper
Infrared spectroscopy
Iron
Ligands
Temperature
oxazolidine
acetonitrile

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Pedersen, A. H., Geoghegan, B. L., Nichol, G. S., Lupton, D. W., Murray, K. S., Martínez-Lillo, J., ... Brechin, E. K. (2017). Hexahalorhenate(IV) salts of metal oxazolidine nitroxides. Dalton Transactions, 46, 5250-5259. https://doi.org/10.1039/C7DT00752C
Pedersen, Anders H. ; Geoghegan, Blaise L. ; Nichol, Gary S. ; Lupton, David W. ; Murray, Keith S. ; Martínez-Lillo, José ; Gass, Ian A. ; Brechin, Euan K. / Hexahalorhenate(IV) salts of metal oxazolidine nitroxides. In: Dalton Transactions. 2017 ; Vol. 46. pp. 5250-5259.
@article{a543150020e449c29b1ebb740be07247,
title = "Hexahalorhenate(IV) salts of metal oxazolidine nitroxides",
abstract = "Eight coordination compounds of formulae [FeII(L•)2][ReIVCl6] (1a), [FeII(L•)2][ReIVBr6] (1b), [CoII(L•)2][ReIVCl6]·CH3CN (2a), [CoII(L•)2][ReIVBr6] (2b), [NiII(L•)(CH3CN)3][ReIVCl6]·CH3CN (3a), [NiII(L•)(CH3CN)3][ReIVBr6]·3CH3CN (3b), [CuII(L•)2][ReIVCl6] (4a)and [CuII(L•)2][ReIVBr6] (4b), where L• is the aminoxyl radical chelating ligand, 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N- oxide, have been synthesised. Structural and magnetic studies reveal metal-radical intramolecular antiferromagnetic interactions in the [MII(L•)2]2+ cations in the iron, cobalt and copper based compounds (1a, 1b, 2a, 2b, 4a and 4b) with the central metal ion low-spin in the case of Fe (1a and 1b) and a gradual, cobalt based, spin-crossover transition present in 2a and 2b. The nickel based compounds, 3a and 3b, were analysed in the dried form (3a(dried) and 3b(dried)) and directly in acetonitrile (3a(solvated) and 3b(solvated)). Microanalysis and IR spectroscopy on 3a(dried) and 3b(dried) suggests the dried samples are best formulated as [NiII(L•)(H2O)3][ReIVX6], where X = Cl (3a(dried)) and Br (3b(dried)). All forms for 3a and 3b exhibit cationic metal-radical ferromagnetic interactions resulting in S = 3/2 ground states. In addition, 3a(dried) exhibits spin-canting behaviour with an ordering temperature of 2.7 K, an open hysteresis loop with a coercive field Hc, = 580 Oe, and a remanent magnetisation Mr = 0.21 μB, resulting in a canting angle of ~1.8°. In contrast 3b(dried) shows no spin-canting behaviour; a maximum in χM vs. T at T = 3 K suggesting long-range antiferromagnetic order. 3a(solvated) and 3b(solvated) show no indication of long-range magnetic ordering, unlike 4a and 4b where anomalies are evident in the low-temperature magnetic susceptibility measurements.",
author = "Pedersen, {Anders H.} and Geoghegan, {Blaise L.} and Nichol, {Gary S.} and Lupton, {David W.} and Murray, {Keith S.} and Jos{\'e} Mart{\'i}nez-Lillo and Gass, {Ian A.} and Brechin, {Euan K.}",
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Pedersen, AH, Geoghegan, BL, Nichol, GS, Lupton, DW, Murray, KS, Martínez-Lillo, J, Gass, IA & Brechin, EK 2017, 'Hexahalorhenate(IV) salts of metal oxazolidine nitroxides', Dalton Transactions, vol. 46, pp. 5250-5259. https://doi.org/10.1039/C7DT00752C

Hexahalorhenate(IV) salts of metal oxazolidine nitroxides. / Pedersen, Anders H.; Geoghegan, Blaise L.; Nichol, Gary S.; Lupton, David W.; Murray, Keith S.; Martínez-Lillo, José; Gass, Ian A.; Brechin, Euan K.

In: Dalton Transactions, Vol. 46, 20.03.2017, p. 5250-5259.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Hexahalorhenate(IV) salts of metal oxazolidine nitroxides

AU - Pedersen, Anders H.

AU - Geoghegan, Blaise L.

AU - Nichol, Gary S.

AU - Lupton, David W.

AU - Murray, Keith S.

AU - Martínez-Lillo, José

AU - Gass, Ian A.

AU - Brechin, Euan K.

PY - 2017/3/20

Y1 - 2017/3/20

N2 - Eight coordination compounds of formulae [FeII(L•)2][ReIVCl6] (1a), [FeII(L•)2][ReIVBr6] (1b), [CoII(L•)2][ReIVCl6]·CH3CN (2a), [CoII(L•)2][ReIVBr6] (2b), [NiII(L•)(CH3CN)3][ReIVCl6]·CH3CN (3a), [NiII(L•)(CH3CN)3][ReIVBr6]·3CH3CN (3b), [CuII(L•)2][ReIVCl6] (4a)and [CuII(L•)2][ReIVBr6] (4b), where L• is the aminoxyl radical chelating ligand, 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N- oxide, have been synthesised. Structural and magnetic studies reveal metal-radical intramolecular antiferromagnetic interactions in the [MII(L•)2]2+ cations in the iron, cobalt and copper based compounds (1a, 1b, 2a, 2b, 4a and 4b) with the central metal ion low-spin in the case of Fe (1a and 1b) and a gradual, cobalt based, spin-crossover transition present in 2a and 2b. The nickel based compounds, 3a and 3b, were analysed in the dried form (3a(dried) and 3b(dried)) and directly in acetonitrile (3a(solvated) and 3b(solvated)). Microanalysis and IR spectroscopy on 3a(dried) and 3b(dried) suggests the dried samples are best formulated as [NiII(L•)(H2O)3][ReIVX6], where X = Cl (3a(dried)) and Br (3b(dried)). All forms for 3a and 3b exhibit cationic metal-radical ferromagnetic interactions resulting in S = 3/2 ground states. In addition, 3a(dried) exhibits spin-canting behaviour with an ordering temperature of 2.7 K, an open hysteresis loop with a coercive field Hc, = 580 Oe, and a remanent magnetisation Mr = 0.21 μB, resulting in a canting angle of ~1.8°. In contrast 3b(dried) shows no spin-canting behaviour; a maximum in χM vs. T at T = 3 K suggesting long-range antiferromagnetic order. 3a(solvated) and 3b(solvated) show no indication of long-range magnetic ordering, unlike 4a and 4b where anomalies are evident in the low-temperature magnetic susceptibility measurements.

AB - Eight coordination compounds of formulae [FeII(L•)2][ReIVCl6] (1a), [FeII(L•)2][ReIVBr6] (1b), [CoII(L•)2][ReIVCl6]·CH3CN (2a), [CoII(L•)2][ReIVBr6] (2b), [NiII(L•)(CH3CN)3][ReIVCl6]·CH3CN (3a), [NiII(L•)(CH3CN)3][ReIVBr6]·3CH3CN (3b), [CuII(L•)2][ReIVCl6] (4a)and [CuII(L•)2][ReIVBr6] (4b), where L• is the aminoxyl radical chelating ligand, 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N- oxide, have been synthesised. Structural and magnetic studies reveal metal-radical intramolecular antiferromagnetic interactions in the [MII(L•)2]2+ cations in the iron, cobalt and copper based compounds (1a, 1b, 2a, 2b, 4a and 4b) with the central metal ion low-spin in the case of Fe (1a and 1b) and a gradual, cobalt based, spin-crossover transition present in 2a and 2b. The nickel based compounds, 3a and 3b, were analysed in the dried form (3a(dried) and 3b(dried)) and directly in acetonitrile (3a(solvated) and 3b(solvated)). Microanalysis and IR spectroscopy on 3a(dried) and 3b(dried) suggests the dried samples are best formulated as [NiII(L•)(H2O)3][ReIVX6], where X = Cl (3a(dried)) and Br (3b(dried)). All forms for 3a and 3b exhibit cationic metal-radical ferromagnetic interactions resulting in S = 3/2 ground states. In addition, 3a(dried) exhibits spin-canting behaviour with an ordering temperature of 2.7 K, an open hysteresis loop with a coercive field Hc, = 580 Oe, and a remanent magnetisation Mr = 0.21 μB, resulting in a canting angle of ~1.8°. In contrast 3b(dried) shows no spin-canting behaviour; a maximum in χM vs. T at T = 3 K suggesting long-range antiferromagnetic order. 3a(solvated) and 3b(solvated) show no indication of long-range magnetic ordering, unlike 4a and 4b where anomalies are evident in the low-temperature magnetic susceptibility measurements.

U2 - 10.1039/C7DT00752C

DO - 10.1039/C7DT00752C

M3 - Article

VL - 46

SP - 5250

EP - 5259

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

ER -

Pedersen AH, Geoghegan BL, Nichol GS, Lupton DW, Murray KS, Martínez-Lillo J et al. Hexahalorhenate(IV) salts of metal oxazolidine nitroxides. Dalton Transactions. 2017 Mar 20;46:5250-5259. https://doi.org/10.1039/C7DT00752C