Thermal analysis and spectroscopic characteristics of tetrabutylammonium tetrachloroferrate(III)

Wyrzykowski, Dariusz; Maniecki, Tomasz P.; Pattek‐Janczyk, A.; Staněk, J.; Warnke, Zygmunt

doi:10.1016/j.tca.2005.05.007

Cited by 28 publications

(20 citation statements)

References 9 publications

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“…The Mössbauer spectrum of 2 consists of four doublets which correspond to iron-containing species in two different oxidation states (see Figure 3 and Table 4). Three doublets with δ values ranging from 1.02 to 1.31 mm/s correspond clearly to the high spin Fe(II) atoms [69,70]. The high values of quadrupole splitting parameters (1.95–2.53 mm/s) manifest a very low symmetry of the Fe(II) environment as expected for the coordination number 5 [69].…”

Section: Resultsmentioning

confidence: 99%

“…The presence of three broadened Fe(II) doublets varying in the values of ΔE Q is probably related to the various degrees of the deformation of the iron(II) environment. The most populated doublet (δ = 0.22 mm/s; ΔE Q = 0.60 mm/s) can be ascribed to a high spin Fe(III) environment in tetrahedral coordination [70]. The increase of the isomer shift in comparison with 1a or 1b can be attributed to the iron spin transition from low to high spin as well as to the different coordination mode of cyanide ion to Fe(III) (Fe III –CN in 1a , b, Fe III –NC in 2 ) [50].…”

Section: Resultsmentioning

confidence: 99%

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Thermal decomposition of [Co(en)3][Fe(CN)6]∙ 2H2O: Topotactic dehydration process, valence and spin exchange mechanism elucidation

Trávníček

Zbořil

Matiková-Maľarová

et al. 2013

Chemistry Central Journal

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BackgroundThe Prussian blue analogues represent well-known and extensively studied group of coordination species which has many remarkable applications due to their ion-exchange, electron transfer or magnetic properties. Among them, Co-Fe Prussian blue analogues have been extensively studied due to the photoinduced magnetization. Surprisingly, their suitability as precursors for solid-state synthesis of magnetic nanoparticles is almost unexplored.In this paper, the mechanism of thermal decomposition of [Co(en)3][Fe(CN)6] ∙∙ 2H2O (1a) is elucidated, including the topotactic dehydration, valence and spins exchange mechanisms suggestion and the formation of a mixture of CoFe2O4-Co3O4 (3:1) as final products of thermal degradation.ResultsThe course of thermal decomposition of 1a in air atmosphere up to 600°C was monitored by TG/DSC techniques, 57Fe Mössbauer and IR spectroscopy. As first, the topotactic dehydration of 1a to the hemihydrate [Co(en)3][Fe(CN)6] ∙∙ 1/2H2O (1b) occurred with preserving the single-crystal character as was confirmed by the X-ray diffraction analysis. The consequent thermal decomposition proceeded in further four stages including intermediates varying in valence and spin states of both transition metal ions in their structures, i.e. [FeII(en)2(μ-NC)CoIII(CN)4], FeIII(NH2CH2CH3)2(μ-NC)2CoII(CN)3] and FeIII[CoII(CN)5], which were suggested mainly from 57Fe Mössbauer, IR spectral and elemental analyses data. Thermal decomposition was completed at 400°C when superparamagnetic phases of CoFe2O4 and Co3O4 in the molar ratio of 3:1 were formed. During further temperature increase (450 and 600°C), the ongoing crystallization process gave a new ferromagnetic phase attributed to the CoFe2O4-Co3O4 nanocomposite particles. Their formation was confirmed by XRD and TEM analyses. In-field (5 K / 5 T) Mössbauer spectrum revealed canting of Fe(III) spin in almost fully inverse spinel structure of CoFe2O4.ConclusionsIt has been found that the thermal decomposition of [Co(en)3][Fe(CN)6] ∙∙ 2H2O in air atmosphere is a gradual multiple process accompanied by the formation of intermediates with different composition, stereochemistry, oxidation as well as spin states of both the central transition metals. The decomposition is finished above 400°C and the ongoing heating to 600°C results in the formation of CoFe2O4-Co3O4 nanocomposite particles as the final decomposition product.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Thermal decomposition of [Co(en)3][Fe(CN)6]∙ 2H2O: Topotactic dehydration process, valence and spin exchange mechanism elucidation

Trávníček

Zbořil

Matiková-Maľarová

et al. 2013

Chemistry Central Journal

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“…A reducing factor can be Cl -ligands, which reduce cobalt(III) in the process of an intramolecular electron transfer. Reducing properties of halogen ligands were observed in reactions of the intramolecular reduction of iron(III) ions present in the tetrachloridoferrate(III) complexes [24][25][26][27]. There is also a possibility of an intermolecular mechanism of the reduction of Co(III), in which chloride ions present outside the inner coordination sphere of the metal ion participate.…”

Section: Thermal Analysismentioning

confidence: 99%

Thermal properties of [Co(en)2Cl2]Cl in solid state. Cis–trans isomerization of the [Co(en)2Cl2]+ complex ion in methanol

Jacewicz

Pranczk

Wyrzykowski

et al. 2014

Reac Kinet Mech Cat

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]Cl complex isomers have been studied using the TG-FTIR and TG-DSC-MS techniques. The measurements were carried out in argon atmosphere over the temperature range 293-873 K. The influence of the configurational geometry on the pathways of thermal transformations was discussed. Furthermore, kinetic studies on the reaction of the cis-trans isomerization of the [Co(en) 2 Cl 2 ]Cl complex salt in methanolic solutions were performed using UV-Vis spectrophotometry at five temperatures in the 293-313 K temperature range. The observed rate constants were computed using the ''Glint'' program based on the global analysis. It has been found that the cis-trans isomerization of [Co(en) 2 Cl 2 ]Cl is a first order reaction. Furthermore, the cis/trans [Co(en) 2 Cl 2 ]Cl isomerization proceeds according to the dissociative mechanism.

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“…Tetraethylammonium tetrachloro-ferrate(III) was investigated by temperature-dependent Mössbauer spectroscopy and became antiferromagnetic with a Néel temperature of 3.0 K [13,14]. A survey of 164 crystal structures included in the November 2003 Cambridge Structural Database (CSD) revealed that the tetrachloroferrate ions have distorted tetrahedral structure with averaged Fe-Cl bond lengths and Cl-Fe-Cl bond angles of 2.204 Å and 109.32°, respectively [15]. It is somewhat surprising to note that there is very little reference in the ME literature to alkali metal tetrachloroferrates, and in particular to the temperature dependencies of the hyperfine and lattice dynamical parameters which have not been reported in detail.…”

Section: Introductionmentioning

confidence: 99%

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

Herber

Nowik

Kostner

et al. 2011

IJMS

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Four 57Fe-labeled tetrachloroferrates(III) of organic cations (1-butyl-3-methylimidazolium, 1-allyl-3-methylimidazolium, 1-methyl-1-propylpyrrolidinium, tetraphenylphosphonium) were examined by temperature-dependent Mössbauer spectroscopy. The hyperfine and dynamic parameters of the iron(III) site were determined. Single crystal X-ray diffraction data of [Ph4P][FeCl4] were collected at four temperatures (295, 223, 173, and 123 K), and the dynamics of the iron atom inferred from the Mössbauer data and the single crystal Ui,j parameters have been compared.

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Thermal analysis and spectroscopic characteristics of tetrabutylammonium tetrachloroferrate(III)

Cited by 28 publications

References 9 publications

Thermal decomposition of [Co(en)3][Fe(CN)6]∙ 2H2O: Topotactic dehydration process, valence and spin exchange mechanism elucidation

Thermal decomposition of [Co(en)3][Fe(CN)6]∙ 2H2O: Topotactic dehydration process, valence and spin exchange mechanism elucidation

Thermal properties of [Co(en)2Cl2]Cl in solid state. Cis–trans isomerization of the [Co(en)2Cl2]+ complex ion in methanol

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

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