Mössbauer Spectroscopic Studies of Ferrocenylaldimines and their TCNQ Complexes

A series of ferrocenylaldimines (Fc-CH=N-R) has been prepared by Schiff base condensation of formylferrocene with polyacenylamines RNH₂ where R = naphthyl, 5,6,7,8-tetrahydronaphthyl, anthracenyl, and pyrenyl groups. This step was followed by oxidation with TCNQ to give [Fc-CH = N-R][TCNQ]² salts. The electronic state of iron in these compounds was investigated by means of⁵⁷Fe Mössbauer spectroscopy.     

Iron speciation in natural hyperacid water investigated by Mössbauer spectroscopy

We have demonstrated the usefulness of the archetypical solid state-technique of Mössbauer spectroscopy to non-invasive studies of the redox and coordination chemistry of iron in a natural hyperacid solution from Iron Mountain, CA. Suitable fast cooling conditions were used to prepare a glass from the natural solution. Measurements of spectra at low temperatures (6 and 15 K) and in large external magnetic fields (6 T) of the glassy, frozen solution revealed a behaviour characteristic of slow paramagnetic relaxation of ferric ions. Analyses of the spectral components are in good agreement with dominance of hexaaquairon(III) ions.     

Mössbauer Spectroscopic Studies of the Hydroxofluorostannate(IV) Complexes

Mössbauer isomer shifts of ¹¹⁹Sn in a series of complexes K₂Sn(OH)_6-mF_m observed at 78 K were ?0.05, ?0.05, ?0.24, ?0.27 and ?0.40 mm s^?1, respectively, for m=0, 2, 4, 5 and 6. These IS values were linearly related to both m and (the average Pauling electronegativity of the ligands): . The IS straight line was compatible within experimental error with the one reported by Parish and Row-botham for the hexahalogenostannate complexes SnX₄Y₂², namely, The revised IS straight line including both series of complexes could be expressed by the equation Quadrupole splittings observed in the complexes of m = 2,4 and 5 were 1.16, 0.80 and 0.73 mm s^?1 respectively. They were linearly related to both m and .     

Fifty Years of Mössbauer Spectroscopy in Solid State Research – Remarkable Achievements,Future Perspectives

Mössbauer spectroscopy was founded more than fifty years ago based on an outstanding discovery by the young German physicist Rudolf Ludwig Mössbauer while working on his Ph.D. thesis. He discovered the recoilless nuclear resonance fluorescence of gamma radiation and was awarded the Nobel Prize in Physics in 1961 as one of the youngest recipients of this most prestigious award. His discovery led to the development of a new technique for measurements of hyperfine interactions between nuclear moments and electromagnetic fields. This method, with highest sharpness of tuning of 10^–13, yields information on valence state, symmetry, magnetic behavior, phase transition, lattice dynamics and other solid state properties.     

Mössbauer and Electrochemical Studies of Bridged Biferrocenes and Biferrocenylenes

A series of neutral and oxidized π-bridged biferrocenes (Fc—x—Fc) and biferrocenylenes (FC(—x—)₂Fc) (x= —CH=CH—, —CH₃,C=CCH₃—) were prepared and their physical properties have been studied by means of Mössbauuer and cyclic voltammetry. The electrode reaction of these bridged ferrocene derivatives appears to involve a consecutive two-step oxidation process. The results also show that the voltage difference between the first and second oxidaton potentials of the bridged biferrocenes was found to be largely exceeded that founded for the corresponding the bridged biferrocenylenes. The Mössbauer data show that the oxidation of doubly bridged Fc(—x—)₂Fc with iodine, DDQ, and TCNQ given the corresponding dioxidized salts only and no stable mixed-valence compounds were found.     

Mössbauer Line Shape of Frozen Aqueous Solutions

Isomer shift of simple lines of the frozen mixture solutions of SnCl5H₂O and K₂SnF₆ were linearly related to mole fraction and, therefore, to average ligand number, ñ. These spectra corresponded to Sn(H₂O)_6-ñF_ñ^{(- ñ)+}. Assuming that quadrupole splitting was also linearly related to ñ, Mössbauer spectra of Sn(ClO₄)₂ solutions containing different amount of HF could be resolved into components.     

Electrodeposition and Mössbauer Spectra of Fe-Zn Alloys on Aluminum Foil

By controlling the current density, pH and temperature of the electrodepositing iron-zinc bath, various compositions of electrodeposited Fe_1-xZn_x (0.95 > x > 0.15) alloys on Al-foil have been prepared. The electronic state, intermetallic phases and magnetic hyperfine interactions have been studied by means of ⁵⁷Fe Mössbauer spectroscopy at 298K for these electrodeposited Fe-Zn alloys. The isomer shifts obtained from the Mössbauer spectral of the alloys increased with increasing Zn content. An alloy containing above 50% Fe, exhibits a linear dependence of the internal magnetic field, Hin, on the Zn content.     

An in‐situ Mössbauer Study of the Formation of Cementite,Fe3C

The formation of cementite, Fe₃C, from thin iron foils has been studied at 550 and 650 °C by means of in‐situ Mössbauer spectroscopy. At 550 °C, the kinetics of the reaction have been determined from time‐resolved experiments performed at different carbon activities. The product formation follows a two‐step process exhibiting two different kinetic regimes. The slow initial stages of the reaction as well as its rapid final part can be described by an Avrami‐type kinetics with a characteristic parameter of n = 3/2.     

Magnetic Hyperfine Mössbauer Spectra of Ferrocenyaldimines-FeCl3 Adducts

Ferrocenylaldimines (Fc-CH=N-R) were prepared by condensation of Schiff base of formylferrocene with polyacenylamines RNH₂; R = naphthyl, anthracenyl and pyrenyl groups. This step was followed by oxidation with FeCl₃ to give [Fc-CH=NR]-FeCl₃ adducts. The electronic state of iron in these adducts was investigated by means of ⁵⁷Fe Mössbauer spectra except for [Fc-CH=N-Pyr]-FeCl₃ showed that only a doublet was observed at ambient temperature. As the temperature was decreased below 200 K, additional magnetic hyperfine splitting was observed characteristic of ferric oxide.     

In situ — High Temperature Mössbauer Spectroscopy of Iron Nitrides and Nitridoferrates

The stoichiometric iron nitrides γ′‐Fe₄N, ε‐Fe₃N and ζ‐Fe₂N were characterized by Mössbauer spectroscopy. The thermal decomposition of ε‐Fe₃N was studied in‐situ by means of a specially developed Mössbauer furnace. We found ε‐Fe₃N to γ′‐Fe₄N and ε‐Fe₃N_x (x ≥ 1.3) as decomposition products and determined the border of γ′/ε transformation at T ? 930 K. Mössbauer spectroscopy was applied to study in‐situ the thermal decomposition of the nitridometalate Li₃[Fe^IIIN₂] and the formation of Li₂[(Li_1‐xFe^I_x)N], the compound with the largest local magnetic field ever observed in an iron containing material. The kinetics of formation and the stability of Li₂[(Li_1‐xFe^I_x)N] was of particular interest in the present study.     

Concentration Dependence of Mössbauer Parameters of SnCl−3 and SnBr−3 Complex Ions

Mössbauer parameters of frozen salt solutions could be correlated with apparent degree of dissociation, γ. KSnCl₃ and KSnBr₃ were dissolved in 0.5 M H₂SO₄, whereas NH₄ SnCl₃ was dissolved in 0.5 M HClO₄. Mössbauer studies were made at different concentrations.