Antimony Fluoride Research Articles

Interphase Formation Versus Fluoride-ion Insertion in Tunnel-Structured Transition Metal Antimonites

Fluoridating reagents are used to model interfacial reactions in fluoride-ion batteries. Topochemical F-ion insertion is evidenced for one-dimensional (1D) tunnel-structured FeSb2O4 but interphase formation comprising antimony (oxy)fluorides is observed for...

Impact of Antimony Fluoride Compounds on Soil Microflora and Methods of Their Detoxification

Impact of Antimony Fluoride Compounds on Soil Microflora and Methods of Their Detoxification

Antimony fluoride (SbF3): A potent hole suppressor for tin(II)‐halide perovskite devices

AbstractTin (Sn2+)‐based halide perovskites have been developed as the most promising alternatives to their toxic Pb‐based counterparts in optoelectronic devices. However, the facile tin vacancy formation and easy oxidization characteristics make Sn2+‐based perovskites highly p‐doped with excessive hole concentrations, which significantly hinder their applications. Herein, we demonstrate a potent hole inhibitor of antimony fluoride (SbF3), which possesses a higher hole‐suppression capability than conventional tin fluoride (SnF2). A small amount of SbF3 allows a wide range of hole‐density modulation with no or less SnF2 addition, thus mitigating the negative effects of using only SnF2. A SnF2/SbF3 co‐additive approach was further developed to achieve high‐performance Sn2+ perovskite thin‐film transistors operated in the enhancement mode with a five‐fold enhancement of the field‐effect mobility and improved operational stability compared to using only SnF2. We expect that the SbF3 hole suppressor and co‐additive approach can provide opportunities for the development of high‐efficiency Sn2+‐perovskite optoelectronic devices.image

(C3N6H7)2SbF5·H2O Exhibiting Strong Optical Anisotropy from the Optimal Arrangement of π-Conjugated (C3N6H7)+ Groups.

An antimony fluoride melamine birefringent crystal, (C3N6H7)2SbF5·H2O, was obtained by introducing the π-conjugated delocalized melamine and antimony trifluoride via a simple aqueous solution evaporation method. It features one-dimensional parallel [C3N6H7]∞ chains further connected by hydrogen bonds originated from [SbF5]2- groups with lone pairs. The experimental optical band gap (4.74 eV) allows it to be used in the ultraviolet region. The first-principles calculations suggest that (C3N6H7)2SbF5·H2O exhibits a large birefringence (∼0.38@550 nm), which is twice larger than that of the commercial CaCO3 crystal. Therefore, introducing the fluoride into π-conjugated melamine may be a good tactic to obtain birefringent crystals with large optical anisotropy.

Cation-anion synergetic interactions achieving tunable birefringence in quasi-one-dimensional antimony(III) fluoride oxalates

Birefringent materials with large optical anisotropy, which can be used to modulate the polarization of light, play a key role in laser techniques and science. However, the exploration studies of new, superior birefringent materials develop extremely slowly due to the lack of effective guidelines for rational design. Herein, three antimony(III) fluoride oxalates, namely, Na2Sb2(C2O4)F6, K2Sb2(C2O4)F6, and Cs2Sb2-(C2O4)2F4·H2O, were successfully synthesized through a rational combination of π-conjugated C2O42− anions and Sb3+ cations with stereochemically active lone pairs. These oxalates feature unique quasi-one-dimensional chain structures that induce large optical anisotropy. Remarkably, Cs2Sb2(C2O4)2-F4·H2O exhibits the largest birefringence (0.325@546 nm) among all reported antimony(III)-based oxysalts. Detailed structural analysis and theoretical calculations confirmed that the optical anisotropy of these oxalates could be tuned through the synergetic interactions of templated cations and anionic functional groups. This work may open the door to efficiently designing excellent birefringent materials and guide the further discovery of other novel structure-driven functional materials.

Peculiarities of ionic mobility and superionic conductivity in Thallium(I) Fluoroantimonates(III). A review

The present analytical review has been revised according to the results of studies on the nature of ionic mobility and conductivity in complex antimony(III) fluorides with thallium cations. The studies have been carried out at the Institute of Chemistry of the Far Eastern Branch of the Russian Academy of Sciences. The relationship between the NMR data, ionic mobility, and conductivity of the compounds has been determined. The suggested mechanisms of the appearance of ionic mobility in the studied antimony fluorides have been investigated, and the factors determining their conductivity have been analyzed. The possibility of using antimony(III) fluorides with thallium(I) cations as functional materials has been discussed.

NH4Sb2(C2O4)F5: A novel UV nonlinear optical material synthesized in deep eutectic solvents

The deep eutectic solvents was first employed to solve the hydrolysis of Sb3+ cations in Sb(III)-oxyacid system to explore new nonlinear optical materials, producing a novel antimony(III) fluoride oxalate named NH4Sb2(C2O4)F5. The title compound featured a 3D noncentrosymmetric structure composed of [Sb2(C2O4)F5]- anionic clusters and NH4+ cations. The cooperative effect of the planar π-conjugated [C2O4]2- anionic groups and the Sb3+ cations with stereochemically active lone pairs induce a relatively strong SHG response (1.1×KH2PO4) and a large birefringence (0.111@546 nm), which was confirmed by detailed theoretical calculations. The overall performances indicate that NH4Sb2(C2O4)F5 is a potential ultraviolet nonlinear optical material. The successful application of deep eutectic solvents in the synthesis for easy hydrolytic materials system opens the door to exploring new inorganic solid functional materials.

Synergistic Effect of π-Conjugated [C(NH2)3] Cation and Sb(III) Lone Pair Stereoactivity on Structural Transformation and Second Harmonic Generation.

The search for nonlinear optical (NLO) crystals with excellent comprehensive properties is a formidable challenge. In this work, two guanidine antimony fluorides, C(NH2)3Sb2F7 and C(NH2)3SbF4, were obtained by conjunction of [C(NH2)3] groups with π-conjugated configuration and stereochemically active Sb3+ cations. Due to the different coordination modes of Sb-F bonds and H-F hydrogen bonds, the crystal structure of C(NH2)3Sb2F7 is centrosymmetric (CS), while C(NH2)3SbF4 is noncentrosymmetric (NCS). Optical measurements show that the UV cutoff wavelengths of the title compounds were both less than 240 nm. Thermal studies indicate that these crystals are stable up to 250 °C. In addition, the second harmonic generation (SHG) response of C(NH2)3SbF4 is 2 times that of KH2PO4 (KDP) with the phase-matchable capacity. Theoretical calculations reveal that the large SHG effects of C(NH2)3SbF4 were attributed to the synergy between the planar [C(NH2)3] units and the distorted [SbF4] groups. These results demonstrate that the guanidine antimony fluorides will have potential value as UV NLO materials.

An Antimony(III) Fluoride Oxalate with Large Birefringence.

Birefringent materials play a key role in modulating the polarization of light and thus in optical communication as well as in laser techniques and science. Designing new, excellent birefringent materials remains a challenge. In this work, we designed and synthesized the first antimony(III) fluoride oxalate birefringent material, KSb2 C2 O4 F5 , by a combination of delocalized π-conjugated [C2 O4 ]2- groups, stereochemical active Sb3+ cations, and the most electronegative element, fluorine. The [C2 O4 ]2- groups are not in an optimal arrangement in the crystal structure of KSb2 C2 O4 F5 ; nonetheless, KSb2 C2 O4 F5 exhibits a large birefringence (Δn=0.170 at 546 nm) that is even better than that of the well-known commercial birefringent material α-BaB2 O4 , even though the latter features an optimal arrangement of π-conjugated [B3 O6 ]3- groups. Based on first-principles calculations, this prominent birefringence should be attributed to the alliance of planar π-conjugated [C2 O4 ]2- anions, highly distorted SbO2 F2 and SbOF3 polyhedra with a stereochemically active lone pair. The combination of lone-pair electrons and π-conjugated systems boosts the birefringence to a large extent and will help the development of high-performance birefringent materials.

Unusual molecular complexes of antimony fluoride dimers with acetonitrile and pyridine: structures and bonding.

The structures of two new molecular complexes of antimony pentafluoride with pyridine (Py) and acetonitrile (AN), SbF5·Py and Sb2F10·AN, and a molecular complex of antimony trifluoride Sb2F6·Py and its ionic derivative [HPy]+[Sb2F7]- in the solid state have been determined by single crystal X-ray structural analysis. The complexes Sb2F10·AN and Sb2F6·Py are the first structurally characterized compounds of dimeric antimony fluorides. To reveal the nature of bonding in the complexes and their stability, DFT computations of the electronic structure and thermodynamic characteristics were performed, in particular the analysis of the electrostatic potentials, the orbital interactions and the topology. The results indicate that the intermolecular Sb⋯F interactions can be described as a network of pnictogen bonds.

NMR spectroscopy of amino acid complexes of antimony(iii) and indium(iii) fluorides

The results of previously published NMR studies of amino acid complexes of antimony (iii) and indium(iii) fluorides are critically analyzed. Correlations between the NMR data, ion mobility, and structure of the complexes in question are considered. The interpretation of the low-temperature 19F NMR spectra of amino acid complexes of antimony(iii) fluorides is corrected and certain figures were changed for better informativity. Mechanisms of the onset of ion mobility in the studied complexes of Sb(iii) and In(iii) fluorides are proposed and the possibility of application of these compounds in the design of functional materials is assessed.

A6Sb4F12(SO4)3 (A = Rb, Cs): Two Novel Antimony Fluoride Sulfates with Unique Crown-like Clusters.

Two new antimony fluoride sulfates named A6Sb4F12(SO4)3 (A = Rb, Cs) with unique crown-like clusters have been successfully synthesized by introducing Sb3+ with a stereochemically active lone pair in the sulfate system through a facile hydrothermal method. The structure regulation induced by the cation sizes results in the symmetry difference in these two title compounds, i.e., Rb6Sb4F12(SO4)3 crystallizing in the polar noncentrosymmetric (NCS) space group of P3 and Cs6Sb4F12(SO4)3 in the centrosymmetric (CS) space group of P1̅. Detailed characterizations, including XRD, thermal behaviors, optical properties, and the theoretical calculations, for these two compounds have been performed. The discovery of the unique crown-like clusters observed in A6Sb4F12(SO4)3 (A = Rb, Cs) enriches the diversity of structures for antimony sulfates systems. Simultaneously, a summary and comparison for all reported antimony halide sulfates has been made to illustrate the synergistic effect of the stoichiometric ratio and cation sizes on the macroscopic centricity and the framework structure, which will guide the systematical discovery of antimony(III)-based functional materials in future.

Thermal Properties and Ion Mobility in Complex Fluorides (C2H6NO2)SbF4 and (C2H6NO2)3[InF6

Thermal properties and ion mobility of (C2H6NO2)SbF4 in antimony(III) fluoride with glycine are studied by DSC, 19F NMR, and 1H NMR methods in the temperature region of 150–450 K. Dynamic processes in complex fluorides (C2H6NO2)SbF4 and (C2H6NO2)3[InF6] are juxtaposed. The NMR data reported earlier for compound (GlyH)3[InF6] are reanalyzed with some corrections. The relationship between NMR data, ion mobility, and the structure of these complexes is discussed. Possible mechanisms of ion mobility developing in complex fluorides Sb(III) and In(III) with glycine are proposed.

Structure and Properties of the Molecular Complex of Antimony(III) Fluoride with γ-Glycine

A binuclear complex of composition 2SbF3·(C2H5NO2) (I) of antimony(III) with the γ-glycine amino acid is prepared. The antimony atoms in this complex are connected to each other by the amino acid ligand. The crystal structure of this complex is determined to be monoclinic, a = 11.5155(3) \(\acute{\overset{\circ}{\mathrm{A}}}\), b = 12.3905(3) \(\acute{\overset{\circ}{\mathrm{A}}}\), c = 8.0906(2) \(\acute{\overset{\circ}{\mathrm{A}}}\), β = 134.261(1)°, Z = 4, space group Cc, which is a novel structural type of antimony(III) fluoride complex compound. The structure is formed by molecular groups SbF3(C2H5NO2)SbF3 connected by secondary bonds into polymeric ribbons parallel to the plane (bc). The ribbons are connected by longer bonds Sb…F (2.674-3.177 \(\acute{\overset{\circ}{\mathrm{A}}}\)) and hydrogen bonds N-H⋯F and C-H⋯F into a three-dimensional framework. Vibrational spectra of I are studied in comparison with those of crystalline γ-glycine. The biological activity of the compound of the antimony(III) fluoride complex with the amino acid is studied in vitro against the following type strains of test cultures: gram-negative bacteria (E. coli, P. aeruginosa), gram-positive bacteria (S. aureus, B. subtilis), and fungi (C. albicans).

Crystal Structure of DL-Valinium Tetrafluoroantimonate(III) Monohydrate

The crystal structure of an antimony(III) fluoride complex of the composition (C5H12NO2)SbF4·H2O (I) involving a cation of α-amino isovaleric acid (DL-valine, Val) is determined. Crystals are monoclinic: a = 12.2024(2) A, b = 6.1636(1) A, c = 15.5167(3) A, Z = 4, space group P21/c. The structure is formed of DL-valinium (C5H12NO2)+ cations, complex [SbF4]nn− anions having a polymeric chain structure, and crystallization water molecules. The [SbF4]nn− complex anions consist of trigonal SbF4E bipyramids joined together by asymmetric bridging Sb–F(3)···Sb bonds. The structural units are organized into a threedimensional framework via N–H···F, N–H···O, and O–H···F hydrogen bonds.

Reactions of antimony compounds with fluorine gas by thermogravimetric and differential thermal analyses and X-ray diffraction analysis

Antimony is one of the key fission products in the reprocessing of spent nuclear fuel by the fluoride volatility method because of the high volatility of antimony fluorides. Since the fluorination reaction of antimony compounds is not well understood, the reaction behavior of antimony compounds with F2 was investigated by thermogravimetric and differential thermal analyses and X-ray diffraction analysis in this study. The target antimony compounds were antimony metal, SbF3, Sb2O3, Sb2O4, and Sb2O5. The fluorination reaction of antimony metal started at 150 °C, and the fluorination product was SbF3. SbF3 volatilized completely by the reaction with F2 above 190 °C; it was considered that volatile SbF5 was formed by the reaction with F2. In the series of fluorination of the antimony oxides, Sb2O3, Sb2O4, and Sb2O5, they started to react with F2 and volatilize at 330 °C as SbF5. During the fluorination of Sb2O3, Sb2O4 was formed temporarily in the course of the reaction. Oxygen released from the fluorination reaction of a part of Sb2O3 would oxidize remained Sb2O3 to Sb2O4. The reaction mechanism for the fluorination of antimony compounds obtained in this study is applicable to evaluate the transfer of antimony in the reprocessing process of the fluoride volatility method.

Crystal structure and ion mobility in the antimony(III) fluoride complex with glycine 2SbF3·(C2H5NO2)

The complex of antimony(III) fluoride with glycine 2SbF3·(C2H5NO2) (I) has been synthesized and investigated by X-ray, and 19F, 1H NMR methods. The structure of I is formed by the molecular SbF3(C2H5NO2)SbF3 groups linked through Sb···F secondary bonds into polymer layers parallel to the (bc) plane. The longer Sb···F bonds (2.674–3.354 Å) and the N–H···F and C–H···F hydrogen bonds link the layers into a three-dimensional framework. The character of ionic motions in fluoride and proton sublattices upon temperature variations in the range 150–435 K has been examined, and their types and temperature ranges, within which they are realized, have been determined. It has been established that ion diffusion in both sublattices of I is observed in the temperature range 400–435 K, and the mechanisms of its emergence are proposed.

Growth, structural, vibrational, mechanical and dielectric studies of KSbF4 crystal

Interest on Antimony Fluoride Compounds (AFC) has been increased for the last two decades due to its superionic conduction and its unusual electro-optic properties. KSbF4 crystal was successfully grown by low temperature solution growth technique. The XRD analysis confirms that the crystal belongs to orthorhombic system with space group Pmmn. From the observed FTIR spectrum the frequencies of the vibrations have been found. Work hardening coefficient of KSbF4 crystal indicates that it belongs to moderately softer category. The dielectric constant (ɛr), the dielectric loss (tanδ) and AC conductivity (σ) were determined as a function of temperature at different frequencies from 100Hz to 1MHz. It has been found out that above 423K, KSbF4 crystal shows superionic behavior, due to fast diffusion motion of fluorine ions.

Extraction of tantalum, niobium, and antimony fluorides

This report deals with the effects of the HF and H2SO4 concentrations and the organic-to-aqueous phase ratio Vorg: Vaq on the distribution of Ta, Nb, and Sb in their extraction with tributyl phosphate and n-octanol from model solutions that are similar in composition to those obtained in columbite-tantalite processing. The recovery of these elements decreases in the order Ta ≫ Sb ≥ Nb. Process conditions for efficient separation of Ta from Nb and Sb have been found.

Thermal properties and ion mobility in complex antimony(III) fluorides with α-amino acids

Differential thermal analysis (DTA) and (19F, 1H) NMR spectroscopy were used to study thermal properties and ion mobility in complex antimony(III) fluorides with amino acids of composition [(CH3)2CH(CH2)CH(NH3)COOH]SbF4 (LeuHSbF4), SbF3[(CH3)2CH(CH2)CH(+NH3)COO−] (SbF3 · Leu), and SbF3[(CH3)2CHCH(+NH3)COO−] (SbF3 · Val). Ionic conductivity in L-leucinium tetrafluoroantimonate(III) was studied using impedance spectroscopy. LeuHSbF4 was found to undergo a diffusion phase transition to a relatively highly conductive state in the range 385–415 K with an attendant loss of thermal stability (softening) of the high-temperature phase.