Mössbauer Spectroscopy and X-ray Diffraction Study of 57Fe-Labeled Tetrachloroferrate(III)-Based Magnetic Ionic Liquids

Herber, Rolfe H.; Nowik, I.; Kostner, Mirco E.; Kahlenberg, Volker; Kreutz, Christoph; Laus, Gerhard; Schottenberger, Herwig

doi:10.3390/ijms12106397

Cited by 17 publications

(12 citation statements)

References 22 publications

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“…Further N···Cl distances in the range of 3.277(2) Å to 3.426(2) Å may be interpreted as weak hydrogen bonds which connect all ions. The title structure is in excellent accord with related structures of double salts in the system aminium + /FeCl 4 -/Cl -. In these structures the chloride anions form the shortest hydrogen bonds whereas the [FeCl 4 ] -anions form exclusively weak hydrogen bonds [8][9][10][11].…”

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confidence: 65%

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Crystal structure of pentakis(diisobutylaminium) dichloride tris(tetrachloridoferrate(III)), C40H100Cl14Fe3N5

Reiß

2013

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialIn a typical experiment 0.487 g (3 mmol) FeCl 3 was dissolved in concentrated hydrochloric acid supported by applying gentle heat. Diisobutylaminiumchloride (0.829 g; 5 mmol) was added to the warm solution and stirred receiving a yellow liquid. At the bottom of the vessel block-shaped, yellow crystals grow within a few days by isothermal evaporation. Experimental detailsAll hydrogen atoms were identified in difference syntheses. (The H atoms of the methyl groups were allowed to rotate with a fixed angle about the C-C bond (HFIX 137 option of the SHELX-2013 program [12]) with U iso (H) set to 1.5U eq (C). Hydrogen atoms belonging to CH 2 groups were placed in calculated positions and were included in the refinement using a riding model with U iso (H) set to 1.2U eq (C). The hydrogen atoms of the NH 2 groups were refined freely with their U iso values set to 1.2U eq (N). DiscussionRecently, simple dialkylaminium salts attracted considerable attention due to their ferroelectric properties [1,2]. Furthermore, salts containing the tetrachloridoferrate(III) anion are of particular interest for their magnetic behavior [3,4]. This contribution is part of our ongoing interest in salts of the system dialkylaminium / halogenometallate [5][6][7]. The asymmetric unit of the title structure consists of five diisobutylaminium cations (dibuH + ), two chloride and three tetrachloridoferrate(III) anions. The bond lengths within the dibuH + cations and the complex [FeCl 4 ] -anions are in the expected ranges. The conformation parameters of the five crystallographically independent dibuH + cations are partly extremely different to fulfill the needs of packing and hydrogen bonding. Strong to medium strong N-H···Cl hydrogen bonds (N···Cl distances range from 3.077(2) Å to 3.238(2) Å) connect the five dibuH + cations with the two chloride anions and one of the [FeCl 4 ] -anions to a moiety with the formal stoichiometry {(dibuH) 5 Cl 2 [FeCl 4 ]} 2+ as shown in the figure. Further N···Cl distances in the range of 3.277(2) Å to 3.426(2) Å may be interpreted as weak hydrogen bonds which connect all ions. The title structure is in excellent accord with related structures of double salts in the system aminium +

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confidence: 65%

“…Furthermore, salts containing the tetrachloridoferrate(III) anion are of particular interest for their magnetic behavior [3,4]. This contribution is part of our ongoing interest in salts of the system dialkylaminium / halogenometallate [5][6][7].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of pentakis(diisobutylaminium) dichloride tris(tetrachloridoferrate(III)), C40H100Cl14Fe3N5

Reiß

2013

Zeitschrift Für Kristallographie - New Crystal Structures

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“…Investigation of the temperature‐dependent 57 Fe Mössbauer effect is useful for elucidating the metal‐atom dynamics in organometallic iron complexes 38. Mössbauer spectra of imidazolium ILs that contained the tetrachloroferrate anion have recently been reported 39. According to the high‐temperature approximation, the recoil‐free fraction ( f ) is given by f =exp(− k 2 < x 2 >)=exp(−6 E r T / M eff c 2 k B θ 2 ), where k is the wave vector of the gamma ray, x 2 is the mean square amplitude of the metal‐atom vibration, θ is the Mössbauer lattice temperature, and M eff is the effective vibrating mass.…”

Section: Resultsmentioning

confidence: 99%

Ionic Liquids of Cationic Sandwich Complexes

Inagaki

Mochida

Takahashi

et al. 2012

Chemistry A European J

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Simple cationic sandwich complexes that contained alkyl- or halogen substituents provided ionic liquids (ILs) with the bis(perfluoroalkanesulfonyl)imide anion. Ferrocenium- and cobaltocenium ILs [M(C(5)H(4)R(1))(C(5)H(4)R(2))][Tf(2)N] (M=Fe, Co) and arene-ferrocenium ILs [Fe(C(5)H(4)R(1))(C(6)H(5)R(2))][Tf(2)N] were prepared and their physical properties were investigated. A detailed comparison of their thermal properties revealed the effects of molecular symmetry and substituents on their melting points. Their viscosity increased on increasing the length of the substituent on the cation and the perfluoroalkyl chain length on the anion. Upon cooling, ILs with low viscosities exhibited crystallization, whereas those with higher viscosities tended to exhibit glass transitions. Most of these salts showed phase transitions in the solid state. A magnetic-switching phenomenon was observed for the paramagnetic ferrocenium IL, which was associated with a liquid/solid transformation, based on the magnetic anisotropy of the ferrocenium cation. (57)Fe Mössbauer spectroscopy was applied to [Fe(C(5)H(4)nBu)(2)][Tf(2)N] to investigate the vibrational behavior of the iron atom in the crystal and glassy states of the ferrocenium IL.

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“…Early work on paramagnetic ionic liquids focused on tetrachloroferrate(III)-based anions, 2,3 since the iron atom exists in a high spin configuration with five unpaired electrons. 4 However, the field has since expanded to include other ligands (e.g., bromide, etc.) and transition metals.…”

Section: Introductionmentioning

confidence: 99%

The Nature of Cation–Anion Interactions in Magnetic Ionic Liquids as Revealed Using High-Pressure Fourier Transform Infrared (FT-IR) Spectroscopy

Burba

Chang

2019

Appl Spectrosc

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Magnetic ionic liquids are a group of magneto-responsive compounds that typically possess high ionic conductivities and low vapor pressures. In spite of the general interest in these materials, a number of questions concerning the fundamental interactions among the ions remain unanswered. We used vibrational spectroscopy to gain insight into the nature of these interactions. Intramolecular vibrational modes of the ions are quite sensitive to their local potential energy environments, which are ultimately defined by cation–anion coordination schemes present among the ions. Ambient pressure Fourier transform infrared (FT-IR) spectroscopy indicates comparable interaction motifs for 1-ethyl-3-methylimidazolium tetrachloroferrate(III), [emim]FeCl4, and 1-ethyl-3-methylimidazolium tetrabromoferrate(III), [emim]FeBr4, magnetic ionic liquids. However, the vibrational modes of [emim]FeCl4 generally occur at slightly higher frequencies than those of [emim]FeBr4. These differences reflect different interaction strengths between the [emim]+ cations and [Formula: see text] or [Formula: see text] anions. This conclusion is supported by gas-phase ab initio calculations of single [emim]FeCl4 and [emim]FeBr4 ion pairs that show longer C–H···Br–Fe interaction lengths compared to C–H···Cl–Fe. Although the IR spectra of [emim]FeCl4 and [emim]FeBr4 are comparable at ambient pressure, a different series of spectroscopic changes transpire when pressure is applied to these compounds. This suggests [emim]+ cations experience different types of interaction with the anions under high-pressure conditions. The pressure-dependent FT-IR spectra highlights the critical role ligands attached to the tetrahalogenoferrate(III) anions play in modulating cation–anion interactions in magnetic ionic liquids.

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Mössbauer Spectroscopy and X-ray Diffraction Study of 57Fe-Labeled Tetrachloroferrate(III)-Based Magnetic Ionic Liquids

Cited by 17 publications

References 22 publications

Crystal structure of pentakis(diisobutylaminium) dichloride tris(tetrachloridoferrate(III)), C40H100Cl14Fe3N5

Crystal structure of pentakis(diisobutylaminium) dichloride tris(tetrachloridoferrate(III)), C40H100Cl14Fe3N5

Ionic Liquids of Cationic Sandwich Complexes

The Nature of Cation–Anion Interactions in Magnetic Ionic Liquids as Revealed Using High-Pressure Fourier Transform Infrared (FT-IR) Spectroscopy

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