Mössbauer spectroscopic study of ferrocene derivatives in the adsorption and liquid-crystalline states

Mössbauer spectra of ferrocene derivatives in the solid, adsorption and liquidcrystalline states were measured at temperatures ranging from 78 to 423 K. The peak intensities of the Mössbauer spectra of ferrocene derivatives adsorbed on silica gel decreased markedly with an increase in temperature. The Mössbauer absorption of [4-(4-methoxyphenoxycarbonyl)-phenoxycarbonyl]alkyl 4-ferrocenylbenzoate at 295 K during the cooling process was observed in what was assumed to be the liquid-crystalline state.     

Mössbauer spectroscopic studies of ferrocene adsorbed on silica gel

Mössbauer spectra of ferrocene adsorbed on silica gel were measured in order to study the state of adsorption. Ferrocene adsorbed on silica gel tended to oxidize in air and form ferricenium ion. It is assumed that the oxidation of adsorbed ferrocene was caused by surface hydroxyls on the silica gel and O₂ in air. It was observed that ferrocene adsorbed weakly at 293 K, although the ferricenium ion adsorbed strongly at 293 K. Thus the adsorption states of ferrocene depend on the experimental condition.     

Mössbauer characterization of iron and cobalt dinitrosyl derivatives of 1,1′-bis(diphenylphosphino)ferrocene

The interest in the synthesis and reactivity of organometallic compounds which have two or more different metals in the same molecule has grown in recent years, due to the new chemical properties that they can present. In this work, we report the Mössbauer characterization of dppfFe(CO)₃ and two novel compounds, dppfFe(NO)₂ and [dppfCo(NO)₂]⁺[SbF₆]^–, where dppf =1,1-bis(diphenylphosphino)ferrocene. The complexes were also characterized by IR and³¹P NMR. The Mössbauer parameters of the dppfFe(NO)₂ and dppfFe(CO)₃, show two iron sites in the same proportions while for [dppfCo(NO)₂ ⁺[SbF₆]^– only one site was observed.     

Mössbauer study of tektites

Room temperature ⁵⁷Fe Mössbauer spectroscopy has been used to investigate the structural and oxidation state of Fe in tektites from different strewn fields. Spectra have been analyzed in terms of two quadrupole splitting distributions corresponding to Fe^3?+? and Fe^2?+?. All tektites show similar distribution of quadrupole splitting. Each distribution has one peak. The Fe^2?+? sites show a narrow region of Mössbauer line shift (δ) and quadrupole splitting (ε), δ?= 1.02–1.10 mm/s and ε?= 0.85–1.00 mm/s relative to α-Fe. These values have been assigned to intermediate coordination between tetrahedral and octahedral. The Fe^3?+? sites show wider regions of hyperfine parameters: δ?= 0.25–0.45 mm/s and ε?= 0.65–0.90 mm/s. The Fe^3?+?/Fe^2?+? ratio was found to be 0.05–0.15.     

Mössbauer and EPR study of nitrosyl hemoglobin

Nitrosyl hemoglobin was prepared by bubbling fresh⁵⁷Fe-enriched rat hemoglobin with NO. S- and X-band EPR spectra at 77 K are typical for anS=1/2 system with an anisotropicg-tensor and exhibit hyperfine interactions of¹⁴N with the electronic spin. Mössbauer spectra at 4.2 and 100 K consist of a superposition of spectra from high- and low-spin Fe(III), deoxygenated hemoglobin and a component corresponding toS=1/2,g=2, hyperfine constantsA _xx /g _{n n} =A _yy /g _{n n} =–19.6 T,A _zz /g _{n n} =6.8 T, quadrupole splitting E _Q=1.5 mm s^–1, isomer shiftI _s=0.42 mm s^–1 and linewidth 0.4 mm s^–1. The spin-lattice relaxation rate at 100 K is <2×10⁶ s^–1.     

Mössbauer study of Brazilian soapstone

Steatite mineral rocks, soapstone, have been studied by X-ray diffraction, optical microscopic analysis (modal analysis), electron probe micro analysis and Mössbauer spectroscopy for characterization, mineral percentages and chemical composition. Mössbauer spectra show both, magnetic interactions corresponding to magnetite and doublets corresponding to talc. chlorite, dolomite and tremolite. The temperature dependence of the quadrupole splitting in dolomite has been explained in terms of crystal field interaction.     

Mössbauer study of Slovak meteorites

⁵⁷Fe Mössbauer spectroscopy was used as an analytical tool in the investigation of iron containing compounds of two meteorites (Rumanová and Ko?ice) out of total of six which had fallen on Slovak territory. In the magnetic fraction of the iron bearing compounds in the Rumanová meteorite, maghemite, troilite and Fe-Ni alloy were identified. In the non-magnetic fraction silicate phases were found, such as olivine and pyroxene. The paramagnetic component containing Fe^3?+? ions corresponds probably to small superparamagnetic particles. The Ko?ice meteorite was found near the town of Ko?ice in February 2010. Its magnetic fraction consists of a Fe-Ni alloy with the Mössbauer parameters of the magnetic field corresponding to kamacite α-Fe(Ni, Co) and troilite. The non-magnetic part consists of Fe^2?+? phases such as olivine and pyroxene and traces of a Fe^3?+? phase. The main difference between these meteorites is their iron oxide content. These kinds of analyses can bring important knowledge about phases and compounds formed in extraterrestrial conditions, which have other features than their terrestrial analogues.     

Mössbauer study of Hungarian phlogopites

Ultramafic xenoliths of mantle origin occur in Hungarian Cretaceous lamprophyres. The aim of the present work was to determine the iron positions and their occupancy in phlogopites originated from ultramafic xenoliths by the help of Mössbauer spectroscopy. On the basis of the evaluation of the Mössbauer spectra Fe _M1 ²⁺ , Fe _M2 ²⁺ , Fe _M2 ³⁺ and Fe _M1 ³⁺ (or in some cases Fe_tet) octahedral and tetrahedral iron sites were identified in the samples. Quantitative analysis was performed for all of the iron sites. We have observed large differences between the Fe²⁺/Fe³⁺ ratio in samples originated from 120–150 km deepness, which phlogopites having been existed at different erosion circumstances. We have found a significantly higher Fe²⁺/Fe³⁺ ratio in phlogopites which had been solidified in 120–150 km depth from the surface of Earth 70–100 million years ago, than those had been crystallized in 60–80 km deepness.     

Mössbauer study of natural wolframites

Natural Wolframite, (Fe _x Mn_1?x )WO₄ withx=0.95 to 0.41, obtained from seven different sites of two quartz-wolframites deposits of Degana and Sirohi in Rajasthan. India, have been studied by Mössbauer spectroscopy down to 20 K. X-ray diffraction studies with a monochromatic Cu radiation (λK_a-1.5405 Å), were carried out to determine the value ofx. The Mössbauer spectra of all seven samples were recored at 300, 200, 100, 50, 40, 30 and 20 K, and were least square fitted for different sites. The Mössbauer parameters are attributed to a high spin ferrous ion in a quite distorted octahedral symmetry, and only one sextet has been resolved below transition temperature.     

Mössbauer study on iron-polygalacturonate coordination compounds

⁵⁷Fe Mössbauer spectroscopy was used to determine the oxidation state and microenvironments of iron in the Fe-polygalacturonate compound prepared by a novel method from pectin. ICP analysis was applied to study the iron content of the coordination compounds. It was found that there are two ferrous and one ferric microenvironments in the compound. In the iron- polygalacturonate compound the ferrous forms occur dominantly. A model for the bonding of Fe in the polygalacturonate chains is proposed.     

Mössbauer study of iron-doped lithium niobate

From Mössbauer spectra of LiNbO₃⁵⁷Fe(III) single crystals under external fields of 4.92 and 6.2 T, the crystal field and hyperfine parameters are determined. Transmission integral fits indicate a Boltzmann population of the Fe(III) electronic levels with a spin temperature equal to the sample temperature. Spectra at external fields of 0 T and 19 mT can be satisfactorily simulated using an effective spin 1/2,g-factors calculated from spin-expectation values and an internal averaged dipole field of 5.5 mT inclined 20 to thec-axis. The simulations indicate cross-relaxation between Nb and Li nuclear spins and the Fe(III) electronic spin.     

Mössbauer study of pure illite and its firing products

Eight illites with an iron content between 0.8% and 8.4%, which X-ray diffraction indicated to be free from interference from other iron-bearing minerals, were studied by Mössbauer spectroscopy at room temperature and 4.2 K. The Fe³⁺ quadrupole splitting varied from 0.59 mm/s for the iron-rich illites (>5 wt.% Fe) to 0.73 mm/s for those poor in iron (wt.% Fe). A distinction of iron sites in the illites with cis- and trans-OH coordination was not possible. The products of firing one illite at temperatures up to 1300 C were also studied and revealed the disappearance of Fe²⁺, the gradual dehydroxylation of illite, and characteristic features of the products formed at higher temperatures.     

Mössbauer and magnetic study of silicon substituted cobalt ferrite

Silicon substituted cobalt ferrites have been investigated for improved performance as stress sensing materials. A series of samples with the formulae CoSi _x Fe_2???x O₄ were prepared using conventional powder ceramic technique. X-ray diffraction patterns were taken to examine spinel crystal structures and energy dispersive spectrometry was done to confirm Si segregations at the grain boundaries. Magnetic and magneto-strictive measurements were carried out to evaluate the material performance. Mössbauer spectra were taken on selective samples to understand the cationic distribution responsible for the modification of properties. The variations are explained on the basis of the strength of the exchange interactions between cations, and anisotropy contributions of cobalt ions. The results demonstrate the possibility of controlling magnetic and magneto-mechanical properties such as Curie temperature and strain derivative through Co and Si substitutions.     

Mössbauer study of EUROFER and VVER steel reactor materials

⁵⁷Fe Mössbauer spectroscopy and X-ray diffractometry were used to study EUROFER or VVER ferritic reactor steels mechanically alloyed with TaC or NbC. Significant changes were found in the Mössbauer spectra and in the corresponding hyperfine field distributions between the ball milled pure steel and that alloyed with TaC or NbC. Spectral differences were also found in the case of use of same carbides with different origin, too. The observed spectral changes as an effect of ball milling of the reactor material steels with carbides can be associated with change in short range order of the constituents of steel.     

Mössbauer and XRD study of intercalated CaFe-layered double hydroxides

N-containing fully saturated (L-prolinate) or aromatic (indole-2-carboxylate) heterocyclic anions were immobilised in CaFe-layered double hydroxide with the dehydration-rehydration method from aqueous ethanol or acetone. The structure of the resulting organic-inorganic hybrids was characterised mainly with powder X-ray diffraction and ⁵⁷Fe Mössbauer spectroscopy, and as supplementary analysis scanning electron microscopy, energy dispersive X-ray spectroscopy with elemental mapping and molecular modelling were also applied. It was found that the solvent mixture used for the synthesis caused enormous difference in the interlayer spacings of the obtained inorganic-organic hybrids.     

Mössbauer and XRD study of hot dip galvanized alloy

Mössbauer spectroscopy has been used to investigate the nature of the Zinc-Iron alloys present within the Hot Dip Galvanized (HDG) layers of steel with a silicon content of 0.35 %. The investigation also studied the impact of the powder coating pretreatment on the nature of the alloy layers. The acid etching process within the pretreatment process in particular would be expected to have a significant impact on the HDG layer. This study utilized ⁵⁷Fe Mössbauer spectroscopy to examine identically processed samples prior to and post pre treatment. XRD and ⁵⁷Fe CEMS measurements were performed on hot galvanized S355J2 + N samples, forming sandwiched structure. Both XRD and CEMS reveal the presence of dominant steel phase in accordance with its estimated occurrence on the surface of the sandwiched samples. Minor Γ-Fe3Zn10, ζ-FeZn15 and solid solution Fe-Zn as well as minor Fe-Si phases could also be identified.     

Mössbauer effect study of the effect of gamma irradiation and heat treatment on montmorillonite

Mössbauer spectroscopy was used to study the effect of gamma irradiation and heat treatment on montmorillonite. Samples were irradiated to gamma-ray doses ranging from 10 Gy up to 30 MGy. Other samples were heated to different temperatures from 400 C up to 1350 C. The lattice distortion caused by gamma irradiation could be followed. The phase transformations which occurred through and above the dehydroxilation temperature range could be traced and identified. The Mössbauer results were confirmed by X-ray diffraction results.     

A Mössbauer study of some new trinuclear Fe−S cluster compounds

The reaction of (u-RS)₂ (XMgS) Fe₂ (CO)₂ with CpFe (CO)₂I gave thirteen new compounds (u-RS) [CpFe (CO)₂S] Fe₂ (CO)₄. Mossbauer spectra were obtained at 80K. Two quadrupote doubles (A set and B set) were present. The ratio of areas between A set and B set was close to 21. The molecule of every compound contained two Fe (2+) which were in the same chemical environment of low spin state with a coordination number of six, and the Mossbauer parameters of the two Fe (2+), IS=0.2–0.3 mm/s, QS=0.7–0.8 mm/s. In addition, the molecule contained a Fe (3+) in low spin state which was proved by ESR. Its Mossbauer parameters, IS=0.4–0.5 mm/s. QS=1.5±1.6 mm/s, The molecular structure of (u-MeS) [u-CpFe (CO)₂S] Fe₂ (CO)₄ was determined by X-ray diffraction, monoclinic form, space group P21/n z=4, unit cell parameters, a=7.90A, b=10.77A, c=22.53A.     

Mössbauer spectroscopy in molecular magnetism

The aim of this paper is to highlight some selected research activities on molecular magnetic materials using Mössbauer spectroscopy as a technique carried out in our laboratory in recent years. The first part of the present article is devoted to the studies of the various magnetic interactions, metal-to-metal electron-transfer phenomenon, glass transition occurring in molecular magnetic materials, whereas the second part deals with the iron(II) high spin (S = 2)–low spin (S = 0) transition phenomenon occurring in some isoxazole ligand based iron(II) compounds as examples with unusually complicated spin transition behaviour. Also, an example of a dinuclear a spin crossover compound of iron(II) is described, where Mössbauer spectroscopy has most convincingly unraveled the mechanism of the spin transition process. Finally, an example from our most recent studies of spin crossover materials exhibiting both thermal spin crossover and liquid crystalline properties in the same temperature interval near room temperature will be presented.