Organic–inorganic interactions revealed by Raman spectroscopy during reversible phase transitions in semiconducting [(C2H5)4N]FeCl4

Brahim, Khaoula Ben; Gzaiel, M. Ben; Oueslati, A.; Khirouni, K.; Gargouri, M.; Corbel, Gwenaël; Bardeau, Jean‐François

doi:10.1039/d1ra02475b

Cited by 15 publications

(6 citation statements)

References 51 publications

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“…The DOS indicates that the band edges of these materials are dominated by the electronic states of the [FeCl 4 ] anion, resulting in the fundamental band gaps of TMA FC and TEA FC being around ∼2.94 and ∼2.90 eV, respectively, corresponding well with the translucent yellow coloring seen in experimental samples in the literature . This band gap is also highly consistent with that reported for the optical band gap determined from solid-state UV–vis spectroscopy and is derived from the inorganic anion …”

Section: Results and Discussionsupporting

confidence: 86%

“…17 This band gap is also highly consistent with that reported for the optical band gap determined from solid-state UV−vis spectroscopy and is derived from the inorganic anion. 49 The frequency and temperature dependence of the permittivity of the two materials revealed the electronic fingerprint of their transition from an ordered dielectric to a locally disordered plastic crystal (Figure 7). The real permittivity (ε′) of TEA FBC at room temperature showed a typical plateau between 10 4 and 1 Hz with a value of around 60 before increasing in the low-frequency range due to dielectric losses and conductivity (Figure 7a).…”

Section: T H I S C O N T E N T Imentioning

confidence: 99%

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Mesophase Transitions in [(C₂H₅)₄N][FeBrCl₃] and [(CH₃)₄N][FeBrCl₃] Ferroic Plastic Crystals

et al. 2022

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Plastic crystals are supramolecular materials that possess a unique high entropy mesophase at elevated temperatures, where a long-range structural symmetry coexists with a local molecular orientational disorder. The transition to mesophase can involve a large entropy change useful for thermal energy storage and influences the temperature range of ferroelectric and piezoelectric properties, important for sensor applications. Synchrotron X-ray diffraction and pair distribution function analysis were used to study the structure, while calorimetry, dielectric, leakage current measurements, and density functional theory were used to investigate the influence of the organic cation on the structure and properties of tetraethylammonium bromotrichloroferrate(III) [(C2H5)4N][FeBrCl3] and tetramethylammonium bromotrichloroferrate [(CH3)4N][FeBrCl3]. The [(C2H5)4N][FeBrCl3] mesophase transition had an entropy change of 151.5 J·K–1·kg–1, while [(CH3)4N][FeBrCl3] had only 49 J·K–1·kg–1. This was explained by the [(C2H5)4N][FeBrCl3] mesophase having less long-range structural symmetry and more local orientational disorder, of both the cations and anions, compared to [(CH3)4N][FeBrCl3]. Both materials exhibited at least two conductive mechanisms below the transition, vacancy-mediated ionic and electronic conduction. The introduction of anion orientational freedom, as opposed to cation orientational freedom, at the mesophase transition was most influential for the electrical properties.

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Section: Results and Discussionsupporting

confidence: 86%

Section: T H I S C O N T E N T Imentioning

confidence: 99%

Mesophase Transitions in [(C₂H₅)₄N][FeBrCl₃] and [(CH₃)₄N][FeBrCl₃] Ferroic Plastic Crystals

et al. 2022

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“…The spectrum shows a strong absorption band in the 3 eV region, which is the typical optical absorption for [FeCl 4 ] − in a tetrahedral geometry. [ 39 ] Other small peaks at 2.75 eV (450 nm) and 2.35 eV (530 nm) are the corresponding absorptions of 1 A 6 to 2 E(a) and 1 A 6 to 2 E(b) states of the N ‐butyl pyridinium ligand. Figure 6b shows the Raman spectrum of [C 4 py][FeCl 4 ].…”

Section: Resultsmentioning

confidence: 99%

Elucidating the Iron‐Based Ionic Liquid [C₄py][FeCl₄]: Structural Insights and Potential for Nonaqueous Redox Flow Batteries

Balischewski,

Bhattacharyya,

Bailey

et al. 2023

Adv Funct Materials

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In this study, a low‐melting organic‐inorganic crystalline ionic liquid compound, N‐butyl pyridinium tetrachlorido ferrate (III) is described. The material can easily be synthesized using a one‐pot approach in an ionic liquid medium. Single‐crystal X‐ray diffraction confirms that the basic inorganic block is [FeCl4]−, which is counterbalanced by an N‐butyl pyridinium cation. The compound exhibits a melting point of 37.6 °C by differential scanning calorimetry, which is among the lowest values for a pyridinium‐based metal‐containing ionic liquid. The material shows promising electrochemical behavior at room temperature in both aqueous and nonaqueous solvents, and at elevated temperatures in its pure liquid state. Given its appreciable solubility in both water and acetonitrile, the compound can act as a redox‐active species in a supporting electrolyte for redox flow battery applications. These classes of low‐melting ionic solids with long‐range order and interesting electrochemical applications are potential candidates for a range of green energy storage and harvesting systems.

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“…High temperature solid state reaction method is a method for preparing SrTiO3 powder by solid state sintering at high temperature. It can be directly synthesized at high temperature and the process is simple [6].…”

Section: High Temperature Solid State Reaction Methodsmentioning

confidence: 99%

“…When the X-ray irradiates the sample surface, the atom will be separated and become a free electron. The change of energy in this process can be expressed by formula (6):…”

Section: Phase Analysismentioning

confidence: 99%

Research and Development of Preparation Technology of Strontium Niobate Titanate Single Crystal

2022

IJETC

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With the continuous warming of semiconductor research, sto has become a candidate to construct a new memristor structure due to its resistance switching phenomenon. By doping sto with metal, researchers can replace SR or Ti elements in sto. For example, sto doped with Nb, Nd, La and other elements becomes an n-type semiconductor. More and more researchers have paid attention to metal doped sto materials. Therefore, the preparation process of strontium niobate doped (SND) single crystals is researched and developed in this paper. Firstly, the optimization and mechanism of hydrothermal synthesis of strontium titanate were studied, and then the preparation process of strontium titanate doped with niobium was analyzed; Finally, the sto single crystal samples doped with 0.05%wt and 0.7%wtnb were characterized. Hall test showed that the single crystal was a donor doped semiconductor. The electrical performance test showed that the strontium niobate single crystal had excellent resistance.

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Organic–inorganic interactions revealed by Raman spectroscopy during reversible phase transitions in semiconducting [(C₂H₅)₄N]FeCl₄

Abstract: The alkylammonium halogenoferrate families are subjected to diverse studies according to their wide field application.

Cited by 15 publications

References 51 publications

Mesophase Transitions in [(C₂H₅)₄N][FeBrCl₃] and [(CH₃)₄N][FeBrCl₃] Ferroic Plastic Crystals

Mesophase Transitions in [(C₂H₅)₄N][FeBrCl₃] and [(CH₃)₄N][FeBrCl₃] Ferroic Plastic Crystals

Elucidating the Iron‐Based Ionic Liquid [C₄py][FeCl₄]: Structural Insights and Potential for Nonaqueous Redox Flow Batteries

Research and Development of Preparation Technology of Strontium Niobate Titanate Single Crystal

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Organic–inorganic interactions revealed by Raman spectroscopy during reversible phase transitions in semiconducting [(C2H5)4N]FeCl4

Abstract: The alkylammonium halogenoferrate families are subjected to diverse studies according to their wide field application.

Cited by 15 publications

References 51 publications

Mesophase Transitions in [(C2H5)4N][FeBrCl3] and [(CH3)4N][FeBrCl3] Ferroic Plastic Crystals

Mesophase Transitions in [(C2H5)4N][FeBrCl3] and [(CH3)4N][FeBrCl3] Ferroic Plastic Crystals

Elucidating the Iron‐Based Ionic Liquid [C4py][FeCl4]: Structural Insights and Potential for Nonaqueous Redox Flow Batteries

Research and Development of Preparation Technology of Strontium Niobate Titanate Single Crystal

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Product

Resources

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Organic–inorganic interactions revealed by Raman spectroscopy during reversible phase transitions in semiconducting [(C₂H₅)₄N]FeCl₄

Mesophase Transitions in [(C₂H₅)₄N][FeBrCl₃] and [(CH₃)₄N][FeBrCl₃] Ferroic Plastic Crystals

Mesophase Transitions in [(C₂H₅)₄N][FeBrCl₃] and [(CH₃)₄N][FeBrCl₃] Ferroic Plastic Crystals

Elucidating the Iron‐Based Ionic Liquid [C₄py][FeCl₄]: Structural Insights and Potential for Nonaqueous Redox Flow Batteries