Unprecedented magnetic behaviour in lanthanide-based ionic liquids

Monson, Todd C.; Stevens, Tyler E.; Leger, Jean L.; Manson, Jamie L.; Lovejoy, Katherine S.; Newsham, Aimee L.; Sesto, Rico E. Del

doi:10.1039/c7cc07060h

Cited by 9 publications

(6 citation statements)

References 25 publications

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“…Hence, from 100 to 300 K, TMBBDI[FeCl 4 ] was superparamagnetic. As reported, most of the MILs were paramagnetic, even for MILs with a higher spin f-block metal, superparamagnetism was rarely observed at temperatures greater than 50 K. 27,29 The superparamagnetism of TMBBDI-[FeCl 4 ] might be related to the π−π stacking biphenyl group. ] as the middle linear section was still observed (upper inset in Figure 2b and Figure S28c).…”

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confidence: 83%

“…3,9,26 Recently, scientists focused on understanding the intermolecular interaction of MILs and PMILs and searched for methods to improve their magnetism. Metal centers with higher spin orbital 4f electrons, such as gadolinium(III), 2 terbium(III), 27 dysprosium(III), 28 and holmium(III), 29 were introduced into the anions for high effective magnetic moment. Although the magnetic susceptibility of the corresponding MILs and PMILs was increased, most of the MILs and PMILs were still paramagnetic at room temperature.…”

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confidence: 99%

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From Paramagnetic to Superparamagnetic Ionic Liquid/Poly(ionic liquid): The Effect of π–π Stacking Interaction

Yuan

Zhao

et al. 2019

ACS Macro Lett.

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Magnetic ionic liquids (MILs) and poly(magnetic ionic liquids) (PMILs) with FeCl4 – as anions usually show weak magnetism, such as paramagnetism or antiferromagnetism, at room temperature. Inspired by the natural inorganic ferromagnet with ordered crystal structures, a soft superparamagnetic ionic liquid (TMBBDI[FeCl4]) and corresponding poly(ionic liquid) (PTMBBDI[FeCl4]) were prepared by introducing π–π stacking biphenyl groups into the organic cations. Both of the compounds exhibited superparamagnetism from 100 to 300 K, while a ferromagnetic hysteresis loop was found at 300 K. Ferromagnetic interactions were observed from zero field cooling and field cooling studies for both TMBBDI[FeCl4] and PTMBBDI[FeCl4]. However, the MIL and PMIL without π–π stacking interaction were paramagnetic without ferromagnetic interaction. The superparamagnetism of the TMBBDI[FeCl4] and PTMBBDI[FeCl4] was ascribed to the π–π stacking interactions between biphenyl groups, which not only shortened the Fe–Fe distance to the ferromagnetic interaction range but also increased the order degree of the molecules.

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confidence: 83%

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confidence: 99%

From Paramagnetic to Superparamagnetic Ionic Liquid/Poly(ionic liquid): The Effect of π–π Stacking Interaction

Yuan

Zhao

et al. 2019

ACS Macro Lett.

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“…As such, the presence of phosphonium cations contributed to the glassy behavior of the MILs without crystallization, while the incorporation of rare earth metals enhanced their magnetic properties. 84 Recently another halometallate anion, the bromotrichloroferrate heteroanion, [FeCl 3 Br] − , has been studied and applied in a series of MILs. 66,85−87 By pairing [FeCl 3 Br] − with symmetrical and unsymmetrical dicationic and tricationic quaternary ammonium cations, MILs with remarkable properties were obtained.…”

Section: Anion-based Milsmentioning

confidence: 99%

Magnetic Ionic Liquids: Current Achievements and Future Perspectives with a Focus on Computational Approaches

Figueiredo,

Voroshylova,

Ferreira

et al. 2024

Chem. Rev.

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Magnetic ionic liquids (MILs) stand out as a remarkable subclass of ionic liquids (ILs), combining the desirable features of traditional ILs with the unique ability to respond to external magnetic fields. The incorporation of paramagnetic species into their structures endows them with additional attractive features, including thermochromic behavior and luminescence. These exceptional properties position MILs as highly promising materials for diverse applications, such as gas capture, DNA extractions, and sensing technologies. The present Review synthesizes key experimental findings, offering insights into the structural, thermal, magnetic, and optical properties across various MIL families. Special emphasis is placed on unraveling the influence of different paramagnetic species on MILs' behavior and functionality. Additionally, the Review highlights recent advancements in computational approaches applied to MIL research. By leveraging molecular dynamics (MD) simulations and density functional theory (DFT) calculations, these computational techniques have provided invaluable insights into the underlying mechanisms governing MILs' behavior, facilitating accurate property predictions. In conclusion, this Review provides a comprehensive overview of the current state of research on MILs, showcasing their special properties and potential applications while highlighting the indispensable role of computational methods in unraveling the complexities of these intriguing materials. The Review concludes with a forward-looking perspective on the future directions of research in the field of magnetic ionic liquids.

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“…Recently, we investigated the physical and magnetic properties of the series [P 666 14 ][RECl 6 ] (RE=Rare Earth) [22] . Further low‐temperature magnetic measurements on [P 666 14 ][RECl 6 ] ILs were subsequently carried out by Monson et al., [23] reporting unusual behavior at temperatures below 50 K, attributed to the trapping of intermediate structures during glass formation. Lanthanide‐containing compounds, featuring ionic liquid properties with melting points at elevated temperatures were reported with a dimeric (m.p.…”

Section: Figurementioning

confidence: 99%

Designing Dimeric Lanthanide(III)‐Containing Ionic liquids

et al. 2023

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Herein, we report on the preparation of liquid dimeric lanthanide(III)-containing compounds. Starting from the design of dimeric solids, we demonstrate that by tuning of anion and cation structures we can lower the melting points below room temperature, whilst maintaining the dimeric structure. Magnetic measurements could establish the spin-spin interactions of the neighboring lanthanide(III) ions in the liquid state at low temperatures, and matched the interactions of the analogous crystalline solid compounds.

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Unprecedented magnetic behaviour in lanthanide-based ionic liquids

Cited by 9 publications

References 25 publications

From Paramagnetic to Superparamagnetic Ionic Liquid/Poly(ionic liquid): The Effect of π–π Stacking Interaction

From Paramagnetic to Superparamagnetic Ionic Liquid/Poly(ionic liquid): The Effect of π–π Stacking Interaction

Magnetic Ionic Liquids: Current Achievements and Future Perspectives with a Focus on Computational Approaches

Designing Dimeric Lanthanide(III)‐Containing Ionic liquids

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