Cooperative Spin‐Crossover Behaviour in Polymeric 1D Fe II Coordination Compounds: [{Fe(tba) 3 }X 2 ]· n H 2 O

A new family of 1D cooperative spin-crossover polymers with general formula [{Fe(tba)3}X2]·nH2O [tba = N-(4H-1,2,4-triazol-4-yl)benzamide; X = CF3SO3–, n = 2 (1), n = 0 (4); BF4–,n = 3 (2), n = 0 (5); 4-CH3C6H4SO3–, n = 3 (3), n = 0 (6)] has been synthesised and characterised using a series of spectroscopic methods, X-ray powder diffraction, magnetic susceptibility measurements and differential scanning calorimetry. The copper analogue of 1, [{Cu(tba)3}(CF3SO3)2]·3H2O (7), has also been synthesised and its crystal structure solved at 293 K. Compound 7 crystallises in the P space group. The bidentate N-(4H-1,2,4-triazol-4-yl)benzamide ligand bridges the copper ions through the 1,2-nitrogen p…

A cyano-bridged bimetallic ferrimagnet: Synthesis, X-ray structure and magnetic study

Mixing of trans-[Mn(cyclam)Cl2]Cl (cyclam = 1,4,8,11-tetraazacyclotetradecane) and potassium hexacyanochromate (K3[Cr(CN)6]) aqueous solutions instantaneously yields a 1D infinite chain complex {[Mn(cyclam)(l-CN)2Cr(CN)4]� H2O}n (1). The crystal structure of 1, crystallizing in the monoclinic system with space group P21/n has been solved from X-ray powder diffraction data following direct space approach and refined by the Rietveld method. The structure analysis of 1 reveals alternating [Cr(CN)6] 3� and [Mn(cyclam)] 3+

Pressure effect on temperature induced high-spin–low-spin phase transitions

The effect of hydrostatic pressure on the transition temperature and the hysteresis widths of first-order spin crossover phase transitions is considered in the frame of the mean field theory and on the basis of the scope of recent pressure experiments. Relevant parameters for a qualitative description of the behaviour of spin transition compounds under pressure are derived and analysed.

A Novel Dinuclear Fe II Spin‐Crossover Complex Based on a 2,2‐Bipyrimidine Bridge Ligand: [Fe(CH 3 bipy)(NCS) 2 ] 2 bpym

The dinuclear iron(II) complex {[Fe(CH3bipy)(NCS)2]2bpym} has been synthesised and its crystal structure determined at 293 K. The magnetic properties display intramolecular antiferromagnetic coupling at 1 bar (J = −4.2 cm−1), and the onset of a pressure-induced spin conversion is observed at 11 kbar. Magnetic field Mossbauer measurements have been carried out at 4.2 K, and indicate that the HS species correspond to [HS-HS] pairs. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Interplay of Antiferromagnetic Coupling and Spin Crossover in Dinuclear Iron(II) Complexes

This article reports on the study of the interplay between magnetic coupling and spin transition in 2,2′-bipyrimidine (bpym)-bridged iron(II) dinuclear compounds. Coexistence of both phenomena has been observed in [Fe(bpym)(NCS)2]2bpym, [Fe(bpym)(NCSe)2]2bpym and [Fe(bt)(NCS)2]2bpym (bpym = 2,2′-bipyrimidine, bt = 2,2′-bithiazoline) by the action of external physical factors namely pressure or electromagnetic radiation. Competition between magnetic exchange and spin crossover has been studied in [Fe(bpym)(NCS)2]2bpym at 6.3 kbar. LIESST experiments carried out in [Fe(bpym)(NCSe)2]2bpym and [Fe(bt)(NCS)2]2bpym at 4.2 K have shown that is possible to achieve dinuclear molecules with different…

The Two‐Step Spin Conversion in a Supramolecular Triple Helicate Dinuclear Iron(II) Complex Studied by Mössbauer Spectroscopy

The triple helicate dinuclear iron(II) complex, [Fe-2(L)(3)](ClO4)(4)center dot 2H(2)O (1), previously reported by Tuna et al. (Chem. Eur. J. 2004, 10, 5737), was prepared and characterised by detailed SQUID and Fe-57 Mbssbauer measurements. Compound 1 exhibits a thermochromic two-step spin conversion at T-SC((1)) ca. 240 K and T-SC((2)) ca. 120 K, but does not switch its spin state further below 20 K as proven by Mossbauer spectroscopy. The sharp variation of the susceptibility below 20 K is due to zero-field splitting of the remaining iron(II) high-spin species. Applied field Fe-57 Mossbauer spectroscopy experiments at 4.2 K indicate that the gradual thermal spin conversion from [HS-HS] p…

Hydroxo Hydrido Complexes of Iron and Cobalt (Sn−Fe−Sn, Sn−Co−Sn): Probing Agostic Sn⋅⋅⋅H−M Interactions in Solution and in the Solid State

Bis(toluene)iron 9 reacts with Lappert's stannylene [Sn[CH(SiMe3)2]2] (4) to form the paramagnetic bis-stannylene complex [[(eta6-toluene)Fe-Sn-[CH(SiMe3)2]2]2] (10). Compound 10 reacts with H2O to form the hydroxo hydrido complex [(eta6-C7H8)(mu-OH)(H)-Fe-[Sn[CH(SiMe3)2]2]2] (12) in high yield; its solid-state structure has been elucidated by X-ray and neutron diffraction analysis. In agreement with the 1H NMR results, 12 contains a hydridic ligand whose exact coordination geometry could be determined by neutron diffraction. The 1H and 119Sn NMR analysis of 12 suggested a multicenter Sn/Sn/H/Fe bonding interaction in solution, based on significantly large values of J(Sn,H,Fe) = 640+/-30 Hz…

Metallatomsynthese, Eigenschaften und Struktur von μ 2 ‐(η 3 ,η 3 ‐Toluol)bis[(η 6 ‐toluol)eisen](Fe‐Fe)

Metal Atom Synthesis, Properties, and Structure of μ2(η3,η3-Toluene)bis[(η6-toluene)iron](Fe-Fe) Metal atom cocondensation of iron atoms and toluene produces the mononuclear iron sandwich compound [(η6-toluene)(η4-toluene)Fe] 1. Complex 1 reacts with a palette of N-containing ligands such as primary, secondary, and tertiary amines as well as pyridine, pyrrolidine, and tmeda to form highly reactive instable intermediates. In the temperature range from -80 to -30°C, the proposed intermediates react with toluene to form the first homoleptic Fe/toluene complex μ2-(η3η3-toluene)-bis[(η6-toluene)iron](Fe-Fe) (3) regardless which N-containing ligand is used. Additionally, 3 is also formed when eth…

High-performance Mössbauer spectroscopy: Criteria, possibilities, limitations

Increasing attention is being paid to non-conventional Mossbauer methods in view of the extension of Mossbauer Spectroscopy (MS) to a broadening field of applications. With such long-lasting experiments the shortening of the measuring time required for a given statistical significance is of major practical importance. It is shown that the statistical utility rateu allows one to determine which experimental parameters have a primary role, and it also enables sucessive optimization. It is pointed out for various MS measurements that the strategy for improving the experimental performance is strongly dependent on the given problem. As examples, time-differential Mossbauer measurements and conv…

Thermodynamics of the spin transition in [FexZn1−x(2-pic)3]Cl2 · EtOH

Abstract With a new type of calorimeter we reinvestigated the specific heat Cp of the mixed crystals [FexZni1−x(2-pic)3]Cl2 · EtOH in the temperature range from 15 to 300 K. On the basis of a phenomenological thermodynamic model the anomaly in the Cp(T) curve of the mixed crystal (x = 0.73) can be quantitatively described as a result of the spin transition (1A1(low spin, LS) → 5T2(high spin, HS)). The parameters of the Gibbs free energy were independently derived from the temperature dependence of the HS fraction γ in [FexZn1−x(2-pic)3]Cl2 · EtOH. The pure iron complex (x = 1) exhibits a two-step spin transition. In the temperature range between the two steps the entropy obtained from the C…

„Supramolekulare“ Festkörperchemie: einander durchdringende diamantartige Gerüststrukturen mit U4+-Ionen und zweizähnigen molekularen P2S62−-S,S′-„Stäben“ in UP4S12

Anomalous pressure dependence of the Lamb-Mössbauer factor in a spin crossover system

The dependence of the f-factor on temperature and on pressure up to 1500 bar has been measured in the spin crossover compound [Fe(2-pic-ND2)3]cl2·EtOD. In the transition region around Tc=146.7 K the pressure dependence of f shows an anomalous increase, which can be explained on the basis of a theoretical model for spin transitions developed by us.

The phase composition of the passive layer on iron

One-Dimensional Iron(II) Compounds Exhibiting Spin Crossover and Liquid Crystalline Properties in the Room Temperature Region

A novel series of 1D Fe(II) metallomesogens have been synthesized using the ligand 5-bis(alkoxy)- N-(4 H-1,2,4-triazol-4-yl)benzamide (C n -tba) and the Fe(X) 2. sH 2O salts. The polymers obey the general formula [Fe(C n -tba) 3](X) 2. sH 2O [X = CF 3SO 3 (-), BF 4 (-); n = 4, 6, 8, 10, 12]. The derivatives with n = 4, 6 exhibit spin transition behavior like in crystalline compounds, whereas those with n = 8, 10, 12 present a spin transition coexisting with the mesomorphic behavior in the room-temperature region. A columnar mesophase has been found for the majority of the metallomesogens, but also a columnar lamellar mesophase was observed for other derivatives. [Fe(C 12-tba) 3](CF 3SO 3) 2…

Variable-temperature X-ray crystal structure determinations of {Fe[tren(6-Mepy)3]}(ClO4)2and {Zn[tren(6-Mepy)3]}(ClO4)2compounds: correlation of the structural data with magnetic and Mössbauer spectroscopy data

Variable-temperature X-ray crystal structure determinations (80–330 K) on compounds {Fe[tren(6-Mepy)3]}(ClO4)2(1-Fe) {tren(6-Mepy)3is tris[3-aza-4-(6-methyl-2-pyridyl)but-3-enyl]amine} and {Zn[tren(6-Mepy)3]}(ClO4)2(1-Zn) {tren(6-Mepy)3is tris[3-aza-4-(6-methyl-2-pyridyl)but-3-enyl]amine} were carried out together with a detailed analysis of the unit-cell volume and parameters in the spin transition region for (1-Fe). Both compounds crystallize in the monoclinic system and retained the space groupP21/cat all measured temperatures. The Fe and Zn atoms are surrounded by six N atoms belonging to imine groups and pyridine groups of the trifurcated ligand, adopting a pseudo-octahedral symmetry. …

Spin-crossover nanocrystals with magnetic, optical, and structural bistability near room temperature.

Spin crossover behavior under pressure of Fe(PM-L)2(NCS)2 compounds with substituted 2′-pyridylmethylene 4-anilino ligands

Abstract New iron(II) spin crossover systems with large aromatic ligands, based on 2′-pyridylmethylene 4-anilino units, have been synthesized and studied. The whole range of spin crossover behavior has been observed, starting from pure high-spin to more or less complete gradual transitions and finally to discontinuous type transitions with both small and large hysteresis. Magnetic measurements under pressure have revealed that two of the compounds exhibit pressure-induced new phases with larger hysteresis than at atmospheric pressure. For one of the compounds the formation of this new phase is irreversible and the hysteresis width is ∼100 K, as compared to 37 K before applying pressure.

Remarkable Steric Effects and Influence of Monodentate Axial Ligands L on the Spin-Crossover Properties of trans-[FeII(N4 ligand)L] Complexes

Iron(II) complexes obtained from tetradentate, rigid, linear N4 ligands have been investigated to appraise the influence of steric effects and the impact of trans-coordinated anions on the spin-transition behavior. As expected, the well-designed ligands embrace the metal center, resulting in octahedral iron(II) complexes where the basal plane is fully occupied by the pyridine/pyrazole N4 ligand, while anions or solvent molecules are exclusively axially coordinated. Precursor complexes, namely, [Fe(bpzbpy)(MeOH)2](BF4)2 (where bpzbpy symbolizes the ligand 6,6'-bis(N-pyrazolylmethyl)-2,2'-bipyridine) and [Fe(mbpzbpy)(MeOH)2](BF4)2 (where mbpzbpy symbolizes the ligand 6,6'-bis(3,5-dimethyl-N-p…

Valenzdelokalisierte und valenzdefinierte FeII-FeIII-Komplexe: der drastische Einfluß der Liganden

Synthesis, crystal structure, EXAFS, and magnetic properties of catena [mu-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate). First crystal structure of an iron(II) spin-crossover chain compound.

[Fe(btzp)3](ClO4)2 (btzp = 1,2-bis(tetrazol-1-yl)propane) represents the first structurally characterized Fe(II) linear chain compound exhibiting thermal spin crossover. It shows a very gradual spin transition (T1/2 = 130 K) which has been followed by magnetic susceptibility measurements and 57Fe Mössbauer spectroscopy. The structure has been solved at 200 and 100 K by single-crystal X-ray analysis. It crystallizes in the trigonal space group P3c1 with Z = 2 Fe(II) units at both temperatures. The molecular structure consists of chains running along the c axis in which the Fe(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands. The main difference between the two forms ap…

Strong Field Iron(II) Complex Converted by Light into a Long-Lived High-Spin State

Synthesis, X-ray crystal structure and magnetic study of a novel μ2-1,1-azido bridged dimeric copper(II) complex

Abstract A new azido derivative of tridentate Schiff base copper(II) complex has been synthesized and characterized. X-ray single crystal structure analysis reveals that the complex [Cu2L2(N3)2(NO3)2] (1), containing 1-(N-pyridylimino)-3-aminopropane (L) as co-ligand, is a dimer in which copper(II) ions are bridged by two azido groups in end-on fashion. The coordination environment around copper(II) is distorted octahedral which is rarely observed among these types of azido bridged copper(II) dimers. Three among the four coordination sites of the basal plane of the octahedron are occupied by the nitrogen atoms of the Schiff base and the fourth site is occupied by a nitrogen atom of a μ2-1,1…

Intersystem crossing in Fe(II) coordination compounds

Fe(II) spin-crossover systems can be quantitatively converted from the low-spin (LS) to the high-spin (HS) state well below the thermal transition temperature by irradiating either into the metal-ligand charge transfer or d-d absorption bands, and even in low-spin systems a transient population of the HS state can be achieved. This fact can be made use of to determine HS → LS relaxation rate constants for a wide variety of Fe(II) spin-crossover and low-spin systems. The HS → LS relaxation shows strong deviations from an Arrhenius behaviour, with nearly temperature-independent tunnelling below ∼70 K and a thermally activated process above ∼100 K. The range of more than 12 orders of magnitude…

Conversion electron Mössbauer study of low carbon steel polarized in aqueous sulfate and sulfite containing sulfate solutions

Abstract The passivation of low carbon steel was studied in aqueous solutions of 0.5 M Na 2 SO 4 (pH = 3.5 and 6.5) and of 0.5 M Na 2 SO 4 + 0.001 M NaHSO 3 (pH 3.5 and 6.5). The used conversion electron Mossbauer spectroscopy (CEMS) with the complementary electrochemical, microscopic and spectrophotometric investigations proved that the presence of sulfite ion induces pitting corrosion. The compositions and thichnesses of the passive films formed during the electrochemical treatments are determined from the conversion electron Mossbauer spectra. γ-FeOOH was found in each case as a major component. At pH = 3.5, the sextet belonging to Fe 3 C appears in the spectra in most cases, and also Fe…

X-ray powder diffraction and LIESST-effect of the spin transition material [Fe(bpp)2](NCS)2·2H2O

Abstract We have studied the X-ray powder diffraction of the spin transition material [Fe(bpp)2](NCS)2 · 2H2O (bpp: 2,6-bis(pyrazol-3-yl)pyridine) at room temperature. Two crystallographic phases have been observed depending on the sample history of this material. The results obtained corroborate the earlier observations from magnetic and calorimetric studies. Relatively prolonged exposure of the sample to X-rays caused a structural change. LIESST and Reverse-LIESST effects, characterised by 57Fe Mossbauer spectroscopy, have been observed in this material.

Pressure effect studies on spin crossover systems

Abstract In the present review article we discuss the results of investigations of the influence of hydrostatic pressure (up to 1.2 GPa) on the spin transition behaviour in coordination compounds of 3d transition metal ions. The systems under investigation are mononuclear spin crossover compounds of iron(II) and chromium(II), dinuclear complexes of iron(II) exhibiting coexistence of intramolecular anti-ferromagnetic coupling and thermal spin crossover, and 1D, 2D and 3D polynuclear spin crossover complexes of iron(II). It is demonstrated that the application of hydrostatic pressure serves as a tool for modifying the ligand field strength in a controlled manner.

Pressure Effect Studies on the Spin‐Transition Behavior of a Dinuclear Iron(II) Compound

Magnetic studies into the effect of different hydrostatic pressures between ambient and 1.03 GPa on the high-spin (HS) i low-spin (LS) transition behavior of the dinuclear iron(II) compound [Fe II 2(PMAT)2](BF4)4·DMF (1, PMAT = 4-amino3,5-bis{[(2-pyridylmethyl)amino]methyl}-4H-1,2,4-triazole, DMF = N,N-dimethylformamide) have been carried out at 2– 300 K. Under ambient pressure, the sample studied exhibits a [HS–HS] to [HS–LS] half spin transition (ST) at T½ = 208 K without any thermal hysteresis. Increasing the pressure above 0.2 GPa causes an increase (initially rapid but above 0.5 GPa more gradual) of T½ as well as a matching reduction in the residual high-spin fraction at room temperatu…

Oxo-Vanadium(IV) Dihydrogen Phosphate: Preparation, Magnetic Study, and Heterogeneous Catalytic Epoxidation

A layered oxo-vanadium(IV) dihydrogen phosphate, {VO(H2PO 4)2} n has been synthesized hydrothermally and characterized by several physicochemical methods. Single-crystal X-ray analysis (crystal system, tetragonal; space group, P4/ ncc; unit cell dimensions, a = b = 8.9632(4), c = 7.9768(32) A) of {VO(H2PO4) 2} n reveals that the compound has an extended two-dimensional structure. The VO2+ moieties are connected through bridging H 2PO4 (-) ions, and this type of connection propagates parallel to the crystallographic ab plane which gives rise to a layered structure. The layers are staked parallel to the crystallographic c axis with a separation between the layers of ca. 4.0 A. Magnetic suscep…

A corrosion study of austenitic and martensitic steels under boiler conditions by means of 57Fe conversion electron mössbauer spectroscopy

Abstract The growth of protective oxide layers on a martensitic FeCr (1.4122) and two austenitic FeCrNi steel samples (1.4550 and Incoloy 800) was studied by means of the 57Fe Conversion Electron Mossbauer Spectroscopy (CEMS). Scanning electron microscopy was applied to characterize the topographical nature of the oxide layers. Following a technical procedure of running-in steam generators, the steel specimens were oxidized in oxygen-free water at 295°C, 142 bar and a pH value between 9 and 10 for periods up to 70 h. In the case of the steels 1.4122 and 1.4550 the only oxide phase detected was non-stoichiometric magnetite, whereas nickel ferrite of nonstoichiometric composition was found…

Verwey-type transition in EuNiP

High temperature 151Eu Mossbauer measurements provide proof for inhomogeneous mixed-valent behaviour in EuNiP. We observed that EuNiP undergoes a Verwey-type charge delocalisation transition when heated above 470 K prior to the structural γ-β phase transition at T ≈ 510 K. This finding confirms the results of photoemission spectroscopy in the isostructural compound EuPdP and of TB-LMTO-ASA band structure calculations. We discuss the role of a van Hove singularity associated with a high density of 4f states close to the Fermi energy in inhomogeneous mixed europium valency, and the microscopic mechanism of γ-β phase transition in compounds analogous to EuNiP.

Synthese und Strukturen neuer Eisen-Sauerstoff-Alkoxid-Cluster

Der Eisen-Sauerstoff-Alkoxy-Cluster [Fe9O3(OC2H5)21]·C2H5OH kann unter unterschiedlichen Bedingungen zu Molekulen umgesetzt werden, denen alle die allgemeine Formel [Fe5O(OR)8(OR′)5] gemeinsam ist. Erwarmt man [Fe9O3(OC2H5)21]·C2H5OH in Toluol, so entsteht [Fe5O(OC2H5)13], das durch Kristallisation abgetrennt werden kann, wohingegen ein Auflosen von [Fe9O3(OC2H5)21]·C2H5OH in tert-Butylamin zum 1 : 2-Addukt [Fe5O(OC2H5)13]·2 t-Bu-NH2 fuhrt. Mit Triethyl- oder Triphenylsilanol entsteht aus [Fe9O3(OC2H5)21]·C2H5OH wieder ein Sauerstoff-Eisencluster des gleichen Motivs: [Fe5O(OC2H5)8{OSi(C2H5)3}5] bzw. [Fe5O(OC2H5)8{OSi(C6H5)3}5]. Die Molekulstruktur [Fe5O(OC2H5)8{OSi(C2H5)3}5], die uber Rontg…

Correlations of the distribution of spin states in spin crossover compounds

Abstract Short range correlations of the distribution of high spin (HS) and low spin (LS) states show up in thermal spin transition curves, decay curves of the light induced metastable HS state (LIESST state), and in structural features during the spin transitions. Correlations are due to short range interactions between the spin crossover molecules. Short range interactions may compete with omnipresent long range interactions and give rise to interesting spin transition phenomena. In this paper, the effect of correlations on the thermal spin transition in the mixed crystal system [Fe x Zn 1− x (pic) 3 ]Cl 2 ·EtOH (pic=picolylamine) is discussed. In particular the step in the thermal transi…

The passivation of steel in sodium sulphate solution studied by CEMS and aes

The passive layer formed on standard steel by anodic oxidation in 0.5 M sodium sulphate solution was found to contain iron only in the trivalent state. The thickness of the layer increases with the applied potential as well as with the time the passivating potential is applied to the sample. These results, compared with the electrochemical data, lead to the suggestion that the passive behaviour is not due to the whole oxidic layer but due to a thin, low lying interfacial layer with a structural disorder.

Synthesis and magnetic properties of an iron 1,2-bisthienyl perfluorocyclopentene photochromic coordination compound

Abstract The coordination compound Fe(BM-4-PTP) 2 (NCS) 2 ⋅2MeOH ( 1 ) including the photoisomerizable ligand BM-4-PTP (1,2-bis(2′-methyl-5′-(pyrid-4″-yl)thien-3′-yl)perfluorocyclopentene) was obtained as an orange powder. The powder turns blue upon photocyclization of the 1,2-bisthienyl photochromic ligand induced by UV light irradiation at room temperature. Photocycloreversion is obtained by visible light irradiation of the material in the solid state. The orange and blue powders were investigated over the temperature range (5–293 K) and pressure range (1 bar–12 kbar) by magnetic susceptibility measurements and variable temperature 57 Fe Mossbauer spectroscopy. The photo-induced colour ch…

Carbon nanotube bags: catalytic formation, physical properties, two-dimensional alignment and geometric structuring of densely filled carbon tubes.

The catalytic CVD synthesis, using propyne as carbon precursor and Fe(NO3)3 as catalyst precursor inside porous alumina, gives carbon nanotube (CNT) bags in a well-arranged two-dimensional order. The tubes have the morphology of bags or fibers, since they are completely filled with smaller helicoidal CNTs. This morphology has so far not been reported for CNTs. Owing to the dense filling of the outer mother CNTs with small helicoidal CNTs, the resulting CNT fibers appear to be stiff and show no sign of inflation, as sometimes observed with hollow CNTs. The fiber morphology was observed by raster electron microscopy (REM), transmission electron microscopy (TEM), and atomic force microscopy (A…

Microstructural and magnetic characterization of dusts from a stone crushing industry in Birbhum, India

Abstract Stone dust sample collected from a stone crushing industry situated at Muhammad Bazar in Birbhum, India, is studied for its physical characterization using various techniques. Morphology and compositional analysis of the stone dust by scanning electron microscopy (SEM) reveal that the dust is an agglomeration of many tiny particles (0.32–2.12 μm), mostly having sharp edges, as well show microstructure heterogeneity. Elements present in the sample are detected by energy dispersive X-ray spectrometry (EDX). The X-ray diffraction (XRD) pattern analysis shows that the sample mainly contains minerals like anorthite, augite, esseneite and albite. An overall antiferromagnetic interaction …

The LIESST state of [Fe(pic)3]Cl2.EtOH – the superstructure under continuous irradiation

The superstructure recently discovered in [Fe(pic)3]Cl2.EtOH at temperatures inside the step region of the high-spin–low-spin transition curve sheds new light on the anomalous transition behaviour in spin crossover compounds. The structure of the metastable LIESST state of [Fe(pic)3]Cl2.EtOH at 10 K has been measured. The decay has been followed by X-ray diffraction using a CCD camera in order to detect reflections of the superstructure building up during the decay. No signal above the noise of the CCD camera was observed, so that even diffuse scattering could not be detected. This finding is in agreement with correlation lengths of pair correlations of molecules in the HS and LS states bei…

Problems of electron detection in Depth-Selective Conversion Electron Mössbauer Spectroscopy

Applications of Depth-Selective Conversion Electron Mossbauer Spectroscopy (DCEMS) are limited by the long measuring times needed for collecting sufficient data statistics. To shorten the recording time, the background should be reduced and the detection efficiency for conversion electrons should be improved. For57Co/57Fe DCEMS, systematic studies were performed to investigate the origin, shape, and structure of the background components in DCEMS data distributions for various samples using channeltrons and low-noise scintillation counters as electron detectors.

A non-heme dinuclear iron(II) complex containing a single, unsupported hydroxo bridge.

Complexation of the tetrapodal pentadentate NN4 ligand 2,6-C5H3N[CMe(CH2NH2)2]2 (I) with iron(II) perchlorate hydrate in methanol, in the presence of N-methylimidazole, produces a diferrous complex with a single, unsupported mu-OH ligand between two {(I)FeII} coordination modules.

Zerstörungsfreie Phasenanalyse dünner Oberflächenschichten mittels Konversionselektronen

By use of an appropriate gamma radiation, conversion electrons may be produced by Mossbauer effect also in a depth below the sample surface deeper than the free path for inelastic electron scattering. Because the Mossbauer spectrum of the conversion electrons reflects the local phase composition, the recording of all electrons escaping from the surface allows an integral phase analysis of a layer of some 10–100 nm thickness. If only electrons within a narrow range of energy are recorded, a depth selective phase analysis is possible. The applicability of these two techniques of conversion electron spectroscopy is demonstrated by a few examples concerning oxidation and passivation of steel. C…

Uncompensated magnetization in the layered molecular antiferromagnet {N(n-C5H11)4[MnIIFeIII(ox)3]}∞

Abstract Studies on the magnetic properties of the molecular antiferromagnetic material {N( n -C 5 H 11 ) 4 [Mn II Fe III (ox) 3 ]} ∞ , carried out by various physical techniques (AC/DC magnetic susceptibility, magnetization, heat capacity measurements and Mossbauer spectroscopy) at low temperatures, have been presented. Different experimental observations complement each other and provide a clue for the observation of an uncompensated magnetization below the Neel temperature and short-range correlations persisting high above T N . It is understood that the honeycomb layered structure of the compound contains non-equivalent magnetic sub-lattices, (Mn II –ox–Fe III A –...) and (Mn II –ox–Fe …

Study of the phase composition of iron-containing Langmuir-Blodgett layers before and after thermal and chemical treatment

Iron-containing Langmuir–Blodgett mono- and multilayers were prepared by depositing ferric stearate onto silicon wafers. Particular care should be taken in order to avoid the presence of alkali ions, which may replace iron ions in the deposited film. By a subsequent heating in air, the fatty acid chains were thermodesorbed. This results in a rather homogeneous coating of the samples by an iron oxide, most probably in the form of crystalline and amorphous γ-FeOOH, as found by conversion electron Mossbauer, photoelectron and microprobe studies. By a subsequent heating in hydrogen gas or exposure to nascent hydrogen, a partial reduction of the iron oxide layer is possible up to the metallic st…

On the Nature of the Plateau in Two-Step Dinuclear Spin-Crossover Complexes

A remarkable feature of the spin-crossover process in several dinuclear iron(II) compounds is a plateau in the two-step transition curve. Up to now, it has not been possible to analyse the spin state of dinuclear pairs that constitute such a plateau, due to the relative high temperatures at which the transition takes place in complexes investigated so far. We solved this problem by experimentally studying a novel dinuclear spin-crossover compound [[Fe(phdia)(NCS)(2)](2)(phdia)] (phdia: 4,7-phenanthroline-5,6-diamine). We report here on the synthesis and characterisation of this system, which exhibits a two-step spin transition at T(c1)=108 K and T(c2)=80 K, displaying 2 K and 7 K wide therm…

CEMS/XPS study of iron stearate Langmuir-Blodgett layers

Langmuir-Blodgett mono- and multilayers of ferric stearate have been formed on oxidized silicon wafers. Thermodesorption of these layers was investigated by conversion electron Mossbauer and photoelectron spectroscopy and some complementary methods. Heating of samples in air up to 523 K leads to a desorption of the fatty acid chains, while the ferric ions are left on the substrate surface. These ions do not cluster laterally like it was found for Cd ions. They form a rather homogeneous, closed oxidic layer. This well defined layer may be used afterwards for further studies of surface reactions as well as interface and intra-layer interactions. The surface iron ions were found to exhibit a r…

High-Spin → Low-Spin Relaxation in [Fe(bpp)2](CF3SO3)2 H2O after LIESST and Thermal Spin-State Trapping—Dynamics of Spin Transition Versus Dynamics of Phase Transition

The iron(II) complex [Fe(bpp)2]-(CF3SO3)2 H2O (bpp = 2,6-bis(pyrazolyl-3-yl)pyridine) shows a thermal spin transition associated with a hysteresis of approximately 140 K width. The transition temperatures T1/2 (where the fraction of HS species γHS = 0.5) are 147 K and ≈285 K in the cooling and heating directions, respectively. The compound shows the LIESST and reverse-LIESST effects at low temperatures. The relaxation of the metastable HS states generated by LIESST was observed quantitatively at temperatures between 77.5 and 85 K by Mossbauer spectroscopy. Metastable HS states can also be generated by rapid cooling of the sample. The relaxation of the metastable HS states formed by thermal …

Time-differential Mössbauer emission spectroscopy: Development of a new spectrometer and first results

A spectrometer for time-differential Mossbauer spectroscopy was developed with a high count rate capability, a good time resolution, and a flexible data handling. Chemical and physical aftereffects following the57Co decay were studied within the cobalt doped systems Turnbulls blue and ZnS.

Light-Induced Excited Spin State Trapping in Iron(II) Complexes

In the course of our studies on the thermally induced high spin (HS) ↔ low spin (LS) transition in iron(II) complexes /1/, \({\!^5{\text{T}}_2}_{\text{g}}\) ↔ \({\!^1{\text{A}}_1}_{\text{g}}\) in the approximation of Oh symmetry, we have observed in 1984 a new photophysical effect /2/: If, at sufficiently low temperature, the solid spin crossover complex is irradiated with green light into the \({\!^1{\text{A}}_1}\)→ \({\!^1{\text{T}}_1}\) ligand field absorption band, the thermodynamically stable LS state can be converted to the metastable HS state and trapped with practically infinite lifetime. We have called this unusual phenomenon “Light-Induced Excited Spin State Trapping (LIESST)”.

Mößbauer- und ESCA-Untersuchungen zur Bildung oxidischer Eisenphasen in wäßrigen Medien unter der Einwirkung organischer Korrosionsinhibitoren

Korrosionsschichten auf Stahl nach Exposition in Wasser mit bestimmter Harte und Chloridgehalt wurden hinsichtlich der Wirksamkeit beigefugter organischer Inhibitoren mittels Mosbauer- und ESCA-Spektroskopie untersucht. Es entstehen relativ dicke Schichten mit einem unerwartet niedrigen Eisengehalt in Form von FeOOH. Die Schichten enthalten merkliche Mengen von Ionen aus der Testlosung und auch Abbauprodukte der Inhibitormolekule. Letztere werden anscheinend in dem korrosiven Medium zersetzt. Es ist anzunehmen, das das Gesamtmolekul zwar den Transport des Inhibitors zum Metall beeinflust, die eigentliche Inhibierung aber allein durch funktionelle Gruppen erfolgt. Mossbauer and ESCA investig…

Spin crossover phenomena in Fe(ii) complexes

The behaviour of spin crossover compounds is among the most striking and fascinating shown by relatively simple molecular species. This review aims to draw attention to the various ways in which spin crossover phenomena are manifested in iron(II) complexes, to offer some rationalisation for these, and to highlight their possible applications. Typical examples have been selected along with more recent ones in order to give an overall view of the scope and development of the area. The article is structured to provide the basic material for those who wish to enter the field of spin crossover.

(Pr4N)4[Ag3Fe2(ECN)12] - Anionennetzwerke mit gegenseitiger Durchdringung

Stark-Feld-Eisen(II)-Komplex konvertiert durch Licht in einen langlebigen High-Spin-Zustand

ChemInform Abstract: Spin Crossover, LIESST, and NIESST-Fascinating Electronic Games in Iron Complexes

Abstract Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic structure phenomena depending on the nature of the coordinating ligand sphere. The change of spin state with temperature (thermal spin crossover”) and light-induced electron transfer processes leading to long-lived metastable states are among the most fascinating electronic games encountered in transition metal compounds and are presently under intensive study by chemists and physicists. The first part of this lecture will survey briefly some highlights of previous work and present recent results on thermal spin crossover in iron(II) compounds. The second part of t…

Study of Fe−Ti and Fe−TiN interfaces by conversion electron Mössbauer spectroscopy

Titanium and titanium nitride-iron interfaces obtained by PVD coated thin films of Ti and TiN onto argon plasma etched iron substrates at various temperatures and negative bias were studied by use of CEMS. It was found that intermixing to Ti with Fe resulted in the appearance of an amorphous FeTi1−x phase. Furthermore, a comparison of CEM spectra of samples before and after heating in UHV has shown rather strong influence of thermal treatments on Fe/Ti as well as Fe/TiN interfaces.

Spin crossover properties of the [Fe(PM-BiA)2(NCS)2] complex - phases I and II

International audience; In the present review, we reexamine the photomagnetic properties of the [Fe(PM-BiA)2(NCS)2], cis-bis(thiocyanato)-bis[(N-2'-pyridylmethylene)-4-(aminobiphenyl)]iron(II), compound which exhibits, depending on the synthetic method, an exceptionally abrupt spin transition (phase I) with a very narrow hysteresis (T1/2O = 168 K and T1/2N = 173 K) or a gradual spin conversion (phase II) occurring at 190 K. In both cases, light irradiation in the tail of the 1MLCT-LS absorption band, at 830 nm, results in the population of the high-spin state according to the light-induced excited spin-state trapping (LIESST) effect. The capacity of a compound to retain the light-induced HS…

Vibrational spectrum of the spin crossover complex [Fe(phen)(2)(NCS)(2)] studied by IR and Raman spectroscopy, nuclear inelastic scattering and DFT calculations.

The vibrational modes of the low-spin and high-spin isomers of the spin crossover complex [Fe(phen)(2)(NCS)(2)] (phen = 1,10-phenanthroline) have been measured by IR and Raman spectroscopy and by nuclear inelastic scattering. The vibrational frequencies and normal modes and the IR and Raman intensities have been calculated by density functional methods. The vibrational entropy difference between the two isomers, DeltaS(vib), which is--together with the electronic entropy difference DeltaS(el)--the driving force for the spin-transition, has been determined from the measured and from the calculated frequencies. The calculated difference (DeltaS(vib) = 57-70 J mol(-1) K(-1), depending on the m…

A new cylindrical, six-membered iron(III) inclusion cluster consisting of three oxo-bridged diiron subunits linked by carboxylate bridges.

Structural and magnetic properties are reported for a new six-membered Fe(III) cluster that consists of an unique combination of oxo and carboxylato bridging groups, by which a cylindrical inclusion cluster with sodium is formed.

The [Fe(etz)6](BF4)2 Spin-Crossover System—Part One: High-Spin ⇌ Low-Spin Transition in Two Lattice Sites

The [Fe(etz),](BF,), spin-cross-over system (etz = 1-ethyl-1 H-tetrazole) crystallizes in space group P1, with the following lattice constants at 298 K: a 10.419(3), b=15.709(1), c = 18.890(2) A = = 71.223(9), =77.986(10), and = 84.62(1)° V = 2862.0(9) A3 and Z = 3. Two nonequivalent lattice sites, one without (site A) and one with (site B) inversion symmetry, are observed. The population of the two sites nA:nB is 2:l. Iron(II) on site A undergoes a thermal low-spin (LS) high-spin (HS) transition with T1/2I, = 105 K. whereas that on site B remains in the high-spin state down to cryogenic temperatures. Application of external pressure of up to 1200 bar between 200 and 60 K does not cause for…

An Iron-Based Molecular Redox Switch as a Model for Iron Release from Enterobactin via the Salicylate Binding Mode

The iron release mechanism from protonated ferric enterobactin [Fe(III)(enterobactinH(3))] via the salicylate binding mode was probed. For this purpose, a tripodal dodecadentate ligand incorporating three salicylamide (OO) and three bipyridine (NN) binding sites was synthesized as well as iron complexes thereof. It was shown that a ferric ion coordinates selectively to the hard salicylamides and a ferrous ion binds to the softer bipyridines. Upon reduction or oxidation, the iron translocates reversibly and intramolecularly from one site to the other, thus displaying switchlike properties. Both states were characterized by cyclic voltammetry and visible and Mössbauer spectroscopy. The Mössba…

Mossbauer study on the distribution of iron in high coercivity chromium dioxide particles

/sup 57/Fe Mossbauer spectroscopy is applied to determine the level of iron doping in high-coercivity CrO/sub 2/ particles. It is found that, compared with the conventional preparation process, the particles contain an increased amount of Fe/sup 3+/ ions in the CrO/sub 2/ crystal lattice, giving rise to higher magnetocrystalline anisotropy. This is reflected in coercivities up to over 900 Oe. All samples contain as a secondary iron-containing phase some (Cr/sub 1-x/Fe/sub x/)/sub 2/O/sub 3/. The valence of the iron doping is predominantly +3; very weak signals in the Mossbauer spectra suggest the existence of Fe/sup 4+/ in an amount 2-3% of the total number of iron atoms. >

Basic Physical Concepts

Mossbauer spectroscopy is based on recoilless emission and resonant absorption of γ-radiation by atomic nuclei. The aim of this chapter is to familiarize the reader with the concepts of nuclear γ-resonance and the Mossbauer effect, before we describe the experiments and relevant electric and magnetic hyperfine interactions in Chaps. 3 and 4. We prefer doing this by collecting formulae without deriving them; comprehensive and instructive descriptions have already been given at length in a number of introductory books ([7–39] in Chap. 1). Readers who are primarily interested in understanding their Mossbauer spectra without too much physical ballast may skip this chapter at first reading and p…

Experimental and Theoretical Investigations on the Synthesis, Structure, Reactivity, and Bonding of the Stannylene-Iron Complex Bis{{bis(2-tert-butyl-4,5,6-trimethyl-phenyl)}Sn}Fe(η6-toluene)

The pi-(arene)bis(stannylene) complex bis(bis(2-tert-butyl-4,5,6-trimethylphenyl)SnFe(eta6-toluene) (Sn-Fe-Sn, 15) is accessible in high yields by a metal-atom-mediated synthesis between iron atoms, toluene, and the stannylene [bis(2-tert-butyl-4,5,6-trimethylphenyl)Sn](3). Complex 15 has a half-sandwich structure with short Fe -Sn bonds (2.432(1) A) and a trigonal-planar coordination at both the Fe and Sn atoms. The distance between the two Sn centers is 3.56 A. Complex 15 is stable under ambient conditions and displays a pi-arene lability, so far rarely observed for (arene)iron complexes; this leads to an irreversible substitution of the arene and formation of fivefold-coordinated zeroval…

DETERMINATION OF THE ALUMINUM CONTENT OF NATURAL AND SYNTHETIC ALUMOGOETHITES USING MÖSSBAUER SPECTROSCOPY

Pressure- and temperature-induced valence tautomeric interconversion in a o-dioxolene adduct of a cobalt-tetraazamacrocycle complex

An electronic switch at the molecular level has been realized by using a class of ionic compounds of the formula [Co(L)(diox)]Y (L = tetraazamacrocyclic ligand, Y = mononegative anion). Such compounds undergo temperature- and pressure-induced intramolecular one-electron transfer equilibria. The transition temperature of interconversion varies with the nature of the counterions Y (Y = PF6, BPh4, I). Surprisingly the effect of the anion on the transition temperature is not only governed by its volume but also by its coulombic interaction.

Mineralogy at Gusev Crater from the Mössbauer spectrometer on the Spirit Rover.

Mössbauer spectra measured on Mars by the Spirit rover during the primary mission are characterized by two ferrous iron doublets (olivine and probably pyroxene) and a ferric iron doublet (tentatively associated to nanophase ferric iron oxide). Two sextets resulting from nonstoichiometric magnetite are also present, except for a coating on the rock Mazatzal, where a hematite-like sextet is present. Greater proportions of ferric-bearing phases are associated with undisturbed soils and rock surfaces as compared to fresh rock surfaces exposed by grinding. The ubiquitous presence of olivine in soil suggests that physical rather than chemical weathering processes currently dominate at Gusev crat…

Modelling of two step high spin⇌low spin transitions using the cluster variation method

Abstract A thermodynamic description of high spin (HS)⇌low spin (LS) transition curves beyond the Bragg–Williams approximation is given using the Kikuchi cluster variation method (CVM). Transition curves of unusual behaviour (i.e. two step transition) are reproduced by short range interaction energies which are present in addition to long range elastic interaction between the spin changing molecules. The correlations in the distribution of the spin changing centers can be expressed analytically. They give rise to a reduced mixing entropy which was found experimentally in compounds with two step transitions.

Mossbauer spectroscopic study of the thermal spin crossover in [Fe(II)(isoxazole)(6)](ClO(4))(2)

The (57)Fe Mossbauer spectroscopy of mononuclear [Fe(II)(isoxazole)(6)](ClO(4))(2) has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S = 0) and high-spin (S = 2) states.Temperature-dependent spin transition curves have been constructed with the least-square fitted data obtained from the Mossbauer spectra measured at various temperatures between 84 and 270 K during a cooling and heating cycle. This compound exhibits an unusual temperature-dependent spin transition behaviour with T(C)(down arrow) = 223 and T(C)(up arrow) = 213 K occurring in the reverse order in comparison to those observed in SQUID observation and many other spin transition compounds. The comp…

Pressure-Induced Spin State Conversion in Antiferromagnetically Coupled Fe(II) Dinuclear Complexes

The effect of pressure on the thermal dependence of the magnetic susceptibility has been investigated in the 2,2‘-bipyrimidine (bpm)-bridged iron(II) complexes of formula {[Fe(L)(NCX)2]2bpm} (X = S...

Dynamics of spin state conversion processes in the solid state

High spin (HS) ⇌ low spin (LS) conversions in transition metal complexes are nonradiative transitions between spin states. In this contribution, we present a study of the temperature and pressure dependence of the HS ⇌ LS intersystem crossing dynamics. For some iron(II) spin-crossover complexes, the rate constants were determined by line shape analysis of57Fe Mossbauer spectra. Their temperature dependence is described by an Arrhenius equation, their pressure dependence is interpreted within absolute rate theory. HS → LS conversion rates at low temperatures were determined from the relaxation of light-induced formation of HS states, monitored by optical spectroscopy. Deviations from a simpl…

Large orbital moments and internal magnetic fields in lithium nitridoferrate(I)

The iron nitridometalates Li2[(Li(1-x)Fe(I)(x))N] display ferromagnetic ordering and spin freezing. Large magnetic moments up to 5.0mu(B)/Fe are found in the magnetization. In Mössbauer effect studies huge hyperfine magnetic fields up to 696 kOe are observed at specific Fe sites. These extraordinary fields and moments originate in an unusual ligand field splitting for those Fe species leading [within local spin density approximation (LSDA)] to a localized orbitally degenerate doublet. Including spin-orbit interaction and strong intra-atomic electron correlation (LDA+SO+U) gives rise to a large orbital momentum.

The influence of water and of alkali promotor on the carbon number distribution of fischer-tropsch products formed over iron catalysts

The carbon number distribution of Fischer-Tropsch products formed over an alkalized precipitated iron catalyst has been studied as a function of the water vapor pressure of the synthesis gas. The carbon number distribution of formed hydrocarbons is characterized by a bimodal Schulz-Flory distribution of growth probabilities P1 ≈ 0.6 and P2 ≈ 0.87 attributed to unpromoted and promoted (alkalized) sites on the catalyst surface. Promoted sites are more stable with respect to oxidation (deactivation) by water than unpromoted sites. The growth probability of unpromoted sites decreases with increasing ratio P/P — Studies using Mossbauer spectroscopy have shown that iron foils treated with water c…

High-spin wheel of a heptanuclear mixed-valent Fe(II,III) complex.

Anwendung der Mößbauer-Spektroskopie auf die Untersuchung von Deckschichten in Naturumlaufkesseln

57Fe-Mosbauer-spektroskopische Transmissions- und Reflexionsmessungen wurden zur Aufklarung der qualitativen und quantitativen Zusammensetzung von Deckschichten auf der Innenseite von Rohren aus Naturumlaufkesseln vorgenommen. Die Deckschichten waren bei 120 bis 174 atu, 320 bis 353 °C, einem pH-Wert zwischen 9,5 und 10,5 und einem Gehalt an P2O5 und SiO2 von < 10 bzw. < 4 mg/l auf den Rohrinnenflachen (Werkstoff 15 Mo 3: 0,12%C, 0,15% Si, 0,5% Mn, 0,04% P, 0,04% S, ⩽ 0,3% Cr, 0,25% Mo, Rest Fe; St. 45. 8. III: < 0,22% C, 0,1% Si, ⩾ 0,45% Mn, 0,05% P, 0,05% S, ⩽ 0,3% Cr, Rest Fe) innerhalb von maximal 127000 h entstanden. Die Mosbauer-spektroskopischen Untersuchungen, unterstutzt durch eine…

A Mössbauer spectroscopic study of salt lake sediments from Qaidam basin

Mossbauer spectroscopy, X-ray diffractometry and chemical fractionation have been used to study the clay smaples in sediments of Charhan playa and Qinghai lake. The spectral components of the Mossbauer spectra of the samples are attributed to Fe2+ ions in chlorite and siderite, Fe3+ ions in clay minerals and hematite, and partly in amorphous ferric hydroxides. The essential difference in the mineral composition of the sediments of both lakes is the presence of siderite in the samples of Char han playa, whereas it is absent in the samples of Qinghai lake. The fraction of the amorphous ferric hydroxides is higher in the sediments of Qinghai lake. Total Fe2+/Fe3+ ratios increase with sediment …

MÖSSBAUER SPECTROSCOPIC STUDIES OF SPIN CROSSOVER COMPOUNDS

Mößbauerspektroskopische Phasenanalyse eisenhaltiger Oberflächenschichten

The [Fe(etz)6](BF4)2 Spin-Crossover System - Part Two: Hysteresis in the LIESST Regime

In the [Fe(etz)6](BF4)2 spincrossover system the iron(II) complexes occupy two nonequivalent lattice sites, sites A and B. Complexes on site A show a thermal high-spin (HS) low-spin (LS) transition at 105 K, whereas complexes on site B remain in the HS state down to 10 K. Complexes on both sites exhibit light-induced spin state conversions (LIESST) at 20 K: LS HS on site A with = 514.5 nm, and HS LS on site B with = 820 nm. The relaxation processes subsequent to the HS LS conversion on site B reveal a light-induced HSLS bistability for the complexes on site B at 70 K. The bistability as well as the absence of a thermal spin transition on site B are attributed to a thermal hysteresis for the…

Spin crossover in metallomesogens

Abstract In this review article are illustrated the strategies developed in order to achieve interplay/synergy between spin transition and liquid crystal transition. The synthesised Fe(II) metallomesogens exhibit different types of interplay between both phase transitions. A classification according to the analysis of the magnetic and structural data has led to the separation of three types of interplay, namely: type i systems with coupled phase transitions, subdivided into three groups a , b and c (in a the structural changes associated with the Cr ↔ LC drive the spin transition while in b these structural changes influence the spin state of the metallic centers but they are not the drivin…

Advances in Mössbauer Emission Spectroscopy

After effects following nuclear transformation have been extensively studied in a large variety of matrices by Mossbauer Emission Spectroscopy (MES). The branching ratios of transient atomic charge states and energetically unstable states of the environment, excitations of electronic ligand field states and populations out of equilibrium within the electronic ground state manifold have been studied. Recent developments and also new insights and understandings of different aspects of the aftereffects of radioactive decay of57Co in semiconductors and molecular crystals are reviewed. A detailed picture of the decay process within the electronic states of the nucleogenic Fe3+ species could be o…

An Inorganic Double Helix Sheathing Alkali Metal Cations: ANb2P2S12(A=K, Rb, Cs), A Series of Thiophosphates Close to the Metal-Nonmetal Boundary-Chalcogenide Analogues of Transition-Metal Phosphate Bronzes?

The new quaternary niobium thiophosphates ANb 2 P 2 S 1 2 (A=K, Rb, Cs) have been prepared and characterized. The title compounds were synthesized by reacting Nb metal, A 2 S, P 2 S 5 , and S at 600-700°C in evacuated silica tubes. They crystallize as "stuffed" variants of the tetragonal TaPS 6 structure type in the tetragonal space group I42d with eight formula units per unit cell and lattice constants a=15.923(2) and c=13.238(3) A for CsNb 2 P 2 S 1 2 , a= 15.887(3) and c=13.132(3) A for RbNb 2 P 2 S 1 2 , and a=15.850(2) and c= 13.119(3) A for KNb 2 P 2 S 1 2 . Their structures are based on double helices formed from interpenetrating, noninteracting spiral chains of binuclear [Nb 2 S 1 2…

Spin Crossover – Quo Vadis?

This retrospective essay is an attempt to span the bridge over eight decades of research on spin crossover (SCO), one of the most fascinating dynamic electron structure phenomena of inorganic coordination chemistry. The occurrence of SCO compounds of 3d transition metal ions and their characterization regarding magnetic, optical, vibrational, structural, and thermodynamic properties are briefly addressed. Selected case studies of chemical influences and physical effects (pressure, magnetic field, light) on SCO behavior are discussed. Particular attention is paid to the importance of Mossbauer spectroscopy in SCO studies. Light-induced excited spin state trapping (LIESST) and related photoph…

Iron(II) Metallomesogens Exhibiting Coupled Spin State and Liquid Crystal Phase Transitions near Room Temperature

Reaction of the ligand 2,2,2-tris(2-aza-3-((5-akloxy)(6-methyl)(2-pyridyl))prop-2-enyl)ethane (C n -tameMe) with Fe(X) 2 . sH 2 O salts afforded a series of spin crossover metallomesogens with general formula [Fe(C n -tame)](X) 2 . sH 2 O (s ≥ 0), with n = 6, 10, 12, 14, 16, 17, 18, or 20 and X =ClO 4 - or BF 4 -. Single crystal X-ray measurements have been performed on the [Fe(C 6 -tameMe)](ClO 4 ) 2 (C 6 -1) derivative at 100 K. The complex C 6 -1 crystallizes in the triclinic system and adopts the Pbca space group. The iron(II) ion is in a distorted octahedral environment shaped by three imine and three pyridine nitrogen atoms of the C n -tameMe ligand. The average Fe-N im and Fe-N py bo…

Electron Transfer, Linkage Isomerization, Bulk Magnetic Order, and Spin-Glass Behavior in the Iron Hexacyanomanganate Prussian Blue Analogue

Formation, phase composition, and transformations of Langmuir-Blodgett multi- and monolayers containing Fe

Mono- and multilayers of ferric stearate were formed by the Langmuir-Blodgett technique. Thermodesorption of the hydrocarbon chains results in well defined thin oxidic films. Their reduction to Fe2+ and α-Fe was followed by conversion electron Mossbauer spectroscopy. Resonance lines can be observed even if the Fe coverage is less than one monolayer.

Pressure effect on a novel spin transition polymeric chain compound

[Fe(hyptrz)3]A2·H2O (hyptrz = 4-(3′-hydroxypropyl)-1,2,4-triazole and A = 4-chlorobenzenesulfonate) represents a novel iron(II) polymeric chain compound. A discontinuous spin transition has been observed by temperature dependent magnetic susceptibility measurements. The spin transition curves are shifted from 181 K to 324 K as the pressure varies from 1 bar to 5.9 kbar. The shapes of these curves are not strongly modified, and this is interpreted as being due to effective cooperative interactions along the chain. This behaviour under pressure can be extended to the family of iron(II)-1,2,4-triazole polymeric chain spin crossover materials.

Bis(3,5-dimethyl-1H-pyrazolyl)selenide--a new bidentate bent connector for preparation of 1D and 2D co-ordination polymers.

The synthesis and description of eight polymeric complexes formed by transition metals with the bifurcated ligand bis(3,5-dimethyl-1H-pyrazolyl)selenide are discussed together with X-ray crystal analysis as well as variable temperature magnetic susceptibility and characterization by Mossbauer spectroscopy. Preferable types of binding patterns of the ligand were determined, which include a variation of the bridging modes (cis- and trans-) and of the separation length, where the latter parameter together with bending of the ligand molecule were found to be dependent on the type of co-ordination geometry of the central atom and the nature of the anion. A strategy for increasing the structure d…

Investigation of structure, stability, phase composition and magnetic ordering in ultrathin iron/nickel films

By thermal and chemical treatment of Langmuir-Blodgett (LB) films, oxidic and metallic Fe and Ni layers can be prepared. The films are characterised, where differences e.g. in the lateral homogeneity are found. The metallic Fe containing samples show a higher corrosion stability as compared with films prepared by other coating techniques. Mixed Fe/Ni oxidic and metallic layers, respectively, are prepared, where the Ni concentration in the oxidic films can be determined as a function of the ratio of initially transferred numbers of LB layers. The phase composition of the metallic Fe changes systematically with the Ni concentration.

A New Valence Tautomerism Example in an Electroactive Ferrocene Substituted Triphenylmethyl Radical

A new molecular system combining an open-shell organic radical that acts as an acceptor group, different from an o-quinone moiety, covalently linked to a ferrocene moiety, acting as the donor group, is shown to exhibit valence tautomerism.

New polynuclear 4,4ˈ-bis-1,2,4-triazole Fe(II) spin crossover compounds

L'interet porte aux materiaux moleculaires du Fe(II) presentant une transition entre un etat haut-spin (HS, S = 2) et un etat bas-spin (LS, S = 0), sous l'effet d'une variation de temperature, de pression ou d'une irradiation lumineuse, n'a cesse de croitre au cours de ces dix dernieres annees [1-4]. La famille des composes du Fe(II) a base de derives du 1,2,4-triazole substitues par un groupe R sur l'azote 4 a ete tres etudiee pour ses proprietes de transition de spin (TS), qui pourraient permettre des applications en electronique moleculaire [5-15, 29, 32, 36, 37]. Nous avons recemment presente le premier compose a TS possedant une structure tridimensionnelle (figure 2). Ce compose de for…

61Ni MÖSSBAUER EFFECT STUDIES OF THE FERRIMAGNETIC SPINEL NiCr2O4 IN AN APPLIED MAGNETIC FIELD

Photomagnetism of Molecular Systems

This article reviews various classes of transition metal compounds which display in the solid state light sensitive electronic structure modifications accompanied by drastic changes of their magnetic and/or optical properties, i.e., photomagnetism. Selected examples from this rapidly expanding field, include spin crossover, stilbenoid and nitrosyl complexes, as well as Prussian blue analogues.

A polymeric two-dimensional mixed-metal network. Crystal structure and magnetic properties of {[P(Ph)4][MnCr(ox)3]}

Abstract The mixed-metal ferromagnet {[P(Ph) 4 ][MnCr(ox) 3 ]} n , where Ph is phenyl and ox is oxalate, has been prepared and a two-dimensional network structure, extended by Mn(II)-ox-Cr(III) bridges, has been determined from single crystal X-ray data. Crystal data: space group R 3 c , a = b =18.783(3), c =57.283(24) A, α=β=90, γ=120°, Z =24 (C 30 H 20 O 12 PCrMn). The magnetic susceptibility data obey the Curie-Weiss law in the temperature range 260–20 K with a positive Weiss constant of 10.5 K. The temperature dependence of the molar magnetization exhibits a magnetic phase transition at T c =5.9 K. The structure is discussed in relation to the strategy for preparing molecular based ferr…

X-ray structure study of the light-induced metastable states of the spin-crossover compound [Fe(mtz)6](BF4)2

Iron(II) complexes exhibiting thermal spin-crossover may be converted from the1A1low-spin (LS) state to the5T2high-spin (HS) state by irradiation with green light (light-induced excited spin-state trapping, LIESST) and from the LS to the HS state by irradiation with red light (reverse LIESST). The lifetime of the metastable LIESST states may be sufficiently long to enable an X-ray diffraction study. The lattice parameters of a single crystal of [Fe(mtz)6](BF4)2(mtz = methyltetrazole) (space groupP21/n) were measured between 300 and 10 K. While one Fe lattice site (A) of the crystal changes from the HS to the LS state near 78 K, the other site (B) remains in the LS state. Using the green lig…

Electronic Relaxation Phenomena Following 57Co(EC)57Fe Nuclear Decay in [MnII(terpy)2](ClO4)2·1/2H2O and in the Spin Crossover Complexes [CoII(terpy)2]X2·nH2O (X = Cl and ClO4):  A Mössbauer Emission Spectroscopic Study

The valence states of the nucleogenic 57Fe arising from the nuclear disintegration of radioactive 57Co by electron capture decay, 57Co(EC)57Fe, have been studied by Mossbauer emission spectroscopy (MES) in the 57Co-labeled systems:  [57Co/Co(terpy)2]Cl2·5H2O (1), [57Co/Co(terpy)2](ClO4)2·1/2H2O (2), and [57Co/Mn(terpy)2](ClO4)2· 1/2H2O (3) (terpy = 2,2‘:6‘,2‘ ‘-terpyridine). The compounds 1, 2, and 3 were labeled with ca. 1 mCi of 57Co and were used as the Mossbauer sources at variable temperatures between 300 K and ca. 4 K. [Fe(terpy)2]X2 is a diamagnetic low-spin (LS) complex, independent of the nature of the anion X, while [Co(terpy)2]X2 complexes show gradual spin transition as the temp…

Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity.

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. Mossbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the Mossbauer spectra on temperature and particle size is explai…

Valence-Delocalized and Valence-Trapped FeIIFeIII Complexes: Drastic Influence of the Ligands

The two macrocyclic ligands H 2 L 1 and H 2 L 2 are not very different, but their Fe II Fe III complexes are remarkably so. [L 1 Fe 2 (μ-OAc) 2 ](ClO 4 ) is valence-delocalized on the Mossbauer time scale over the range 1.8-364 K, whereas [L 2 Fe 2 (μ-OAc)(OAc)(H 2 O)](ClO 4 )·2H 2 O is valence-trapped even at room temperature. The difference in properties of these complexes is also reflected in their electronic spectra, in their electrochemical and magnetic behavior, and in their structures.

Effect of metal dilution on the light-induced spin transition in [FexZn1-x(phen)2(NCS)2] (phen = 1,10-phenanthroline)

International audience; The thermal and light-induced spin transitions in [FexZn1-x(phen)2(NCS)2] (phen = 1,10-phenantholine) have been investigated by magnetic susceptibility, photomagnetism and diffuse reflectivity measurements. These complexes display a thermal spin transition and undergo the light-induced excited spin state trapping (LIESST) effect at low temperatures. For each compound, the thermal spin transition temperature, T1/2, and the relaxation temperature of the photo-induced high-spin state, T(LIESST), have been systematically determined. It appears that T1/2 decreases with the metal dilution while T(LIESST) remains unchanged. This behaviour is discussed on the basis of the ki…

ANOMALOUS SPIN STATES OF IRON (II) IN MÖSSBAUER EMISSION SPECTRA OF [57 Co(2-CH3-phen),] (ClO4)2.2 H2O AND [57Co(2-CH3O-phen)3] (ClO4)2.H2O

Rapid cooling experiments and use of an anionic nuclear probe to sense the spin transition of the 1D coordination polymers [Fe(NH2trz)3]SnF6n x H2O (NH2trz=4-amino-1,2,4-triazole).

[Fe(NH(2)trz)(3)]SnF(6)n H(2)O (NH(2)trz=4-amino-1,2,4-triazole; n=1 (1), n=0.5 (2)) are new 1D spin-crossover coordination polymers. Compound 2 exhibits an incomplete spin transition centred at around 210 K with a thermal hysteresis loop approximately 16 K wide. The spin transition of 2 was detected by the Mossbauer resonance of the (119)Sn atom in the SnF(6) (2-) anion primarily on the basis of the evolution of its local distortion. Rapid-cooling (57)Fe Mossbauer and superconducting quantum interference device experiments allow dramatic widening of the hysteresis width of 2 from 16 K up to 82 K and also shift the spin-transition curve into the room temperature region. This unusual behavio…

Pressure effect studies in molecular magnetism

We report on temperature dependent magnetic susceptibility and Mossbauer effect studies of the influence of hydrostatic pressure (up to 1.2 GPa) on dynamic electronic structure phenomena in 3d transition metal coordination compounds. The systems under investigation are mononuclear spin crossover compounds of iron (II) and chromium (II), dinuclear complexes of iron (II) exhibiting coexistence of intramolecular antiferromagnetic coupling and thermal spin crossover, 1D, 2D and 3D polynuclear spin crossover complexes of iron (II), a valence tautomeric system of cobalt (II) showing a thermal transition from a high spin [CoII (semiquinone)] to a low spin [CoII (catecholate)] species on lowering t…

Hierarchical Self-Assembly of Supramolecular Spintronic Modules into 1D- and 2D-Architectures with Emergence of Magnetic Properties

Hierarchical self-assembly of complex supramolecular architectures allows for the emergence of novel properties at each level of complexity. The reaction of the ligand components A and B with Fe II cations generates the (2 K 2) grid-type functional building modules 1 and 2, presenting spin-tran- sition properties and preorganizing an array of coordination sites that sets the stage for a second assembly step. Indeed, binding of La III ions to 1 and of Ag I ions to 2 leads to a 1D columnar superstructure 3 and to a wall-like 2D layer 4, respectively, with concomitant modulation of the magnetic properties of 1 and 2. Thus, to each of the two levels of structural complexity generat- ed by the t…

Icems and dcems study of Fe layers evaporated onto Al and Si

Thin layers of57Fe (2.5 nm, 10 nm and 70 nm thickness), vacuum evaporated onto Al and Si plates, have been investigated by conversion electron Mossbauer spectroscopy (CEMS). The measurements were performed employing both a proportional counter and a channeltron for conventional and ultrahigh-vacuum integral CEMS (UHV-ICEMS) studies, respectively, and a channeltron for depth-selective CEMS (DCEMS). The phase analysis of the layers on base of experimental results has indicated the presence of metallic iron and one or two iron compounds, ascribed to iron reaction products formed with the residual gas during evaporation. These products are most likely rather stable iron nitrides, are more or le…

Fascinating electronic games in iron complexes

Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic-structure phenomena, depending on the nature of the coordinating ligand sphere. The change of spin state with temperature («thermal spin-crossover»), light-induced electron transfer processes leading to long-lived metastable charge and spin states (e.g., «LIESST» effect), are some of the fascinating electronic games encountered in transition metal compounds, which are presently under extensive study by chemists and physicists. Mossbauer spectroscopy plays a dominant role in the investigation of such phenomena in iron compounds, as will be demonstrated in this paper. This wo…

Structural and magnetic diversity in metal-dicyanamido polymer moieties: Paramagnetic and antiferromagnetic 1D chain compound and weakly ferromagnetic 2D motif

Abstract The reaction of M(NO 3 ) 2 · x H 2 O (M = Cu, Ni and Co; x  = 3 for Cu and x  = 6 for Co/Ni), imidazole (Im) and sodium dicyanamide (dca) afforded the complexes [M(Im) 2 (dca) 2 ] (where M = Cu for 1 , M = Ni for 2 , and M = Co for 3 ). All of them have been characterized structurally by single crystal X-ray diffraction measurements. X-ray analysis reveals that the dicyanamido ligand features the μ 1,3 bridging mode that led to the formation of two-dimensional structure of complex 1 while complexes 2 and 3 attribute an infinite one-dimensional chain like structure to generate the fascinating molecular assemblies. The {N(CN) 2 } − ligands present in the complexes 2 and 3 are coordin…

Mixed spin-state [HS-LS] pairs in a dinuclear spin-transition complex: confirmation by variable-temperature 57Fe Mössbauer spectroscopy.

Exquisite sensitivity of Mossbauer spectroscopy for tiny local molecular distortion is demonstrated in [FeII2(pmat)2](BF4)4?DMF: high-spin (HS) iron(II) in [HS-HS] and in [LS-HS] (low-spin–high-spin) pairs is clearly distinguished (see picture) for the first time without the need to apply a magnetic field. This dinuclear complex clearly shows that spin crossover via a [LS-HS] species is promoted by the use of a highly constrained bridging ligand (the bis-terdentate pmat).

Synthesis, crystal structure and magnetic properties of bis[μ-bis(3-(pyridin-2-yl)-1,2,4-triazole-N′,N1,N2)] bis[triaqua nickel(II)] tetranitrate

Abstract A new dinuclear nickel(II) coordination compound of formula Ni2(Hpt)2(H2O)6(NO3)4 (Hpt=3-(pyridin-2-yl)-1,2,4-triazole) was synthesized. The structure was solved at 298 K by single-crystal X-ray analysis. Bisμ-bis(3-(pyridin-2-yl)-1,2,4-triazole-N′,N1,N2) bistriaqua nickel(II) tetranitrate (C14H24N12O18Ni2) crystallizes in the triclinic space group P-1, a=7.2266(1), b=9.9144(1), c=11.2647(1) A, α=66.854(1)°, β=74.000(1)°, γ=86.400(2)°, V=712.42(1) A3, Z=1 (dinuclear units), 2823 reflections (1 > 2σ(I)), R1=0.0442, wR2=0.1197. The Ni(II) ions are bridged by two neutral Hpt ligands coordinating via N1 and N2 in the equatorial plane, Ni(1)-Ni(1)′=4.098(1) A. The Hpt bridging mode is a…

The influence of hydrostatic pressure on hysteresis phase transition in spin crossover compounds

Abstract The effect of hydrostatic pressure on the transition temperature and the hysteresis widths of first order spin crossover phase transitions has been studied. A decrease as well as an increase of the hysteresis width with increasing pressure was reported in the literature. The increase of width with increasing pressure contradicts the expectation derived from mean field theory. We remeasured the pressure dependence of the temperature hysteresis of the compound [Fe(phy)2](BF4)2 (phy=1, 10-phenanthroline-2-carbaldehydephenylhydrazone). The spin transition temperatures at ambient temperature are T ↑ 1/2 =289±1 K, T ↓ 1/2 =283±1 K . An increase of the hysteresis width of d Δ T 1/2 / d p=…

Durch Temperatur, Druck oder Licht induzierter Spinübergang in einer supramolekularen Fe‐[2×2]‐Gitterverbindung

Spin Crossover, Liesst, and Niesst-Fascinating Electronic Games in Iron Complexes

Abstract Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic structure phenomena depending on the nature of the coordinating ligand sphere. The change of spin state with temperature (thermal spin crossover”) and light-induced electron transfer processes leading to long-lived metastable states are among the most fascinating electronic games encountered in transition metal compounds and are presently under intensive study by chemists and physicists. The first part of this lecture will survey briefly some highlights of previous work and present recent results on thermal spin crossover in iron(II) compounds. The second part of t…

Does the solid-liquid crystal phase transition provoke the spin-state change in spin-crossover metallomesogens?

Three types of interplay/synergy between spin-crossover (SCO) and liquid crystalline (LC) phase transitions can be predicted: (i) systems with coupled phase transitions, where the structural changes associated to the Cr LC phase transition drives the spin-state transition, (ii) systems where both transitions coexist in the same temperature region but are not coupled, and (iii) systems with uncoupled phase transitions. Here we present a new family of Fe(II) metallomesogens based on the ligand tris[3-aza-4-((5-C(n))(6-R)(2-pyridyl))but-3-enyl]amine, with C(n) = hexyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, R = hydrogen or methyl (C(n)-trenH or C(n)-trenMe), which affords examp…

Phase composition of Fe-containing Langmuir-Blodgett layers after thermal treatment in a reactive atmosphere

By the Langmuir-Blodgett technique, mono- and multilayers of ferric stearate were drawn onto silicon wafers. They were thermodesorbed in air at 250–300°C, and the layers formed in this way were found to consist of γ-FeOOH with defective stoichiometry. By heating in H2, the layers can be reduced to Fe2− and even to α-Fe. The latter is magnetically ordered and highly corrosion resistant. Chloride ions, however, induce fast corrosion. FeCl2, formed by this corrosion, is rather unstable and transforms to an Fe3+ phase. The high corrosion resistance of the metallic Fe layer is assumed to be due to its excellent homogeneity. The experiments were performed using XPS, AES, CEMS, and SEM.

Maghemite polymer nanocomposites with modulated magnetic properties

A method is presented for the production of maghemite polymer nanocomposites with modulated magnetic properties. Magnetic nanocomposites prepared using this method show regular variation in the magnetic blocking temperature from 2 K to 300 K, and variation in the saturation magnetization from 0 to 50 emu g � 1 (Fe2O3). The method is based on the in situ formation of maghemite nanoparticles in nitrogen-base polymer matrixes. The particle size can be varied regularly from 1.5 nm to 16 nm by changing the ratio of iron loading in the polymer and/or the Fe(II)/Fe(III) ratios. The particles are isolated and uniformly distributed within the matrix. The mate

Thermal and Light-Induced Spin Transition in [Fe(bpen)X2] (bpen = 1,6-Bis(2-pyridyl)-2,5-diazahexane, X = NCS-, NCSe-)

The thermal and light-induced spin transitions in [Fe(bpen)(NCS)2] and [Fe(bpen)(NCSe)2] have been investigated by means of magnetic susceptibility and Mossbauer measurements. The HS → LS transition in [Fe(bpen)(NCS)2] is detected at temperatures below 120 K (T1/2 [when the fraction of high-spin species γHS = 0.5] = 68 K) with a residual HS fraction of 8% at 20 K. The transition is fairly abrupt and no hysteresis is observed, in contrast to earlier studies (ref. [8]). The generation of metastable HS states in [Fe(bpen)(NCS)2] is achieved by rapid cooling of the sample and by irradiating the compound at low temperatures with light of appropriate wavelengths (LIESST). The HS → LS relaxation o…

Electronic, vibrational, and structural properties of a spin-crossover catecholato-iron system in the solid state: theoretical study of the electronic nature of the doublet and sextet states.

As a functional model of the catechol dioxygenases, [(TPA)Fe(Cat)]BPh4 (TPA = tris(2-pyridylmethyl)amine and Cat = catecholate dianion) exhibits the purple-blue coloration indicative of some charge transfer within the ground state. In contrast to a number of high-spin bioinspired systems, it was previously shown that, in the solid state, [(TPA)Fe(Cat)]BPh4 undergoes a two-step S = 1/2 = S = 5/2 spin-crossover. Therefore, the electronic and vibrational characteristics of this compound were investigated in the solid state by UV/Vis absorption and resonance Raman spectroscopies over the temperature range of the transition. This allowed the charge-transfer transitions of the low-spin (LS) form …

The state of iron in andalusite

Iron in andalusite (Al2SiO5) with concentrations of 1.5 … 4.3 wt-% has been reported in the literature to occupy mainly Al1 sites as Fe3+, and only small portions occupy Al2 sites as Fe3+ and Fe2+. In no case a magnetic hyperfine splitting has been found at temperatures above 77 K.

An ESCA and Mössbauer study of the oxide layer formed on steel in water containing chromate and chloride ions

Abstract The formation of oxidic layers on steel in chromate solutions was studied by photo-electron and Mossbauer spectroscopy. To simulate more aggressive realistic systems, some chloride ions were added to the solution. The layers formed under these conditions were found to be thicker by an order of magnitude than those formed in the absence of chloride ions. They probably consist of ferric and chromic oxides of the corundum type (Fe 1−2 Cr x ) 2 O 3 , with the Cr : Fe ratio being depth dependent. The oxide layer is subdivided into small regions behaving superparamagnetically. This heterogeneity of the layer is ascribed to the attack by the chloride ions. The structure of the oxides foun…

XPS study of leached glass surfaces

Abstract By use of a special deconvolution algorithm, it was possible to decompose the XPS O 1s signal into several components reflecting different oxygen bonds. The influence of exposure in vacuo, environmental atmosphere, distilled water, and in a polish solution as corrosive media on the surface of different glasses has been studied. The O 1s signals of fused silica, Na 2 O· n SiO 2 glasses, a BaO·SiO 2 and a BaOB 2 O 3 SiO 2 glass (Schott SK 16) were analyzed. On the glass surfaces, leached layers were formed and analyzed qualitatively and semiquantitatively by XPS and optical and infrared methods. As a reference, virgin surfaces of samples broken in ultrahigh vacuum have been used. T…

Pressure effect on the magnetism of layered copper(II) compounds with interlayer spacing up to 40.7 Å: Nature of the magnetic ordering

The influence of pressure on the structure and magnetic properties of the layered hybrid compounds Cu 2 (OH) 3 (n-C m H 2 m + 1 CO 2 ), zH 2 O is investigated for m = 10 and 12. It is shown that the distance between magnetic copper(II) layers, up to 40.7 A, is not significantly modified and that the temperature of the ferromagnetic ordering decreases linearly with pressure increase. We present a new analysis of the susceptibility data, based on the scaling theory of phase transitions, which clearly shows up a crossover from a high-temperature two-dimensional (2D) behavior to a 3D regime at about 30 K, around 10 K above the long-range ordering temperature. A model of quantum ferromagnetic la…

Phosphoraneiminato complexes of manganese and cobalt with heterocubane structure

The phosphoraneiminato complexes [MnBr(NPEt3)]4 (1) and [M4Br5{NP(NMe2)3}3] with M = Mn (2) and M = Co (3) are prepared by melting reactions from the anhydrous metal dibromides with the silylated phosphaneimines Me3SiNPR3 (R = Et, NMe2) in the presence of potassium fluoride. All complexes are characterized by crystal structure analyses. 1 forms an only slightly distorted Mn4N4 heterocubane skeleton with an approximate Td symmetry and short Mn…Mn distances of average 295.7 pm. In the structures of 2 and 3 one μ3-NPEt3 ligand of 1 is replaced by one bromine atom with μ3-function. This leads to the novel heterocubane type M4N3Br with approximate C3 symmetry. The deformation of the cubic skelet…

First Example of Coexistence of Thermal Spin Transition and Liquid-Crystal Properties.

The rodlike FeIII complex of an N-alkyloxysalicylidenyl-N'-ethyl-N-ethylenediamine ligand, shown as a computer model in the picture, is the first compound in which spin-crossover (SC) and liquid-crystalline (LC) properties coexist. This synergy should allow the magnetic and optical properties of SC compounds to be combined with the sensitivity of the LC state to electromagnetic fields.

Thermal and Light-Induced Spin Transition in the High- and Low-Temperature Structure of [Fe0.35Ni0.65(mtz)6](ClO4)2

The thermal and light induced spin transition in [Fe(0.35)Ni(0.65)(mtz)(6)](ClO(4))(2) (mtz = 1-methyl-1H-tetrazole) was studied by (57)Fe Mössbauer spectroscopy and magnetic susceptibility measurements. In addition to the spin transition of the iron(II) complexes the compound undergoes a structural phase transition. The high-temperature structure could be determined by X-ray crystallography of the isomorphous [Fe(0.25)Ni(0.75)(mtz)(6)](ClO(4))(2) complex at room temperature. The X-ray structural analysis shows this complex to be rhombohedric, space group Rthremacr;, with a = 10.865(2) Å and c = 23.65(1) Å with three molecules in the unit cell. The transition to the low-temperature structur…

Quantitative XPS analysis of leached layers on optical glasses

The corrosion of optical glasses often reduces the utility of uncoated glasses as well as the adhesion of resistive coatings deposited onto corroded glasses. Photoelectron spectroscopy (XPS) was applied to study glass surfaces with respect to their surface corrosion. In particular, leaching by the influence of polish slurries, pure water, air and even residual gases inside a vacuum device was studied in detail. Pure quartz glass and different sodium and barium silicate glasses were broken in ultrahigh vacuum (4 × 10−10 mbar) for the determination of sensitivity factors of the different XPS signals. It was found that a quantitative determination of the surface composition of corroded and lea…

Some Special Applications

We have learned from the preceding chapters that the chemical and physical state of a Mossbauer atom in any kind of solid material can be characterized by way of the hyperfine interactions which manifest themselves in the Mossbauer spectrum by the isomer shift and, where relevant, electric quadrupole and/or magnetic dipole splitting of the resonance lines. On the basis of all the parameters obtainable from a Mossbauer spectrum, it is, in most cases, possible to identify unambiguously one or more chemical species of a given Mossbauer atom occurring in the same material.

Interpretation of Mössbauer Parameters of Iron Compounds

The task of this section is to show that for the interpretation of Mossbauer parameters — in the present case of electron densities, field gradients and magnetic hyperfine fields — bonding effects can play an important role, and free-ion or crystal field approaches may be a poor approximation.

Spin-Crossover and Liquid Crystal Properties in 2D Cyanide-Bridged FeII−MI/II Metalorganic Frameworks

Novel two-dimensional heterometallic Fe(II)-M(Ni(II), Pd(II), Pt(II), Ag(I), and Au(I)) cyanide-bridged metalorganic frameworks exhibiting spin-crossover and liquid crystal properties, formulated as {FeL(2)[M(I/II)(CN)(x)](y)}·sH(2)O, where L are the ligands 4-(4-alkoxyphenyl)pyridine, 4-(3,4-dialkoxyphenyl)pyridine, and 4-(3,4,5-trisalkoxyphenyl)pyridine, have been synthesized and characterized. The physical characterization has been carried out by means of EXAFS, X-ray powder diffraction, magnetic susceptibility, differential scanning measurements, and Mössbauer spectroscopy. The 2D Fe(II) metallomesogens undergo incomplete and continuous thermally induced spin transition at T(1/2) ≈ 170 …

A Mössbauer study of the crystalline structure of the passive film formed on iron in aqueous sulfate solution containing sulfite in low concentration

Electrochemically induced passivation of evaporated, enriched 57Fe in 0.5 mol dm−3 Na2SO4 + 0.001 mol dm−3 NaHSO3 aqueous solution (pH 6.5) was followed by conversion electron Mossbauer spectroscopy. The transformation of amorphous iron oxide or hydroxide into crystalline γ-FeOOH could be observed with the increase of the polarization time. The comparison of the original quantity of evaporated, enriched 57Fe layer on the surface of the samples with the dissolved iron, measured in the solutions after the polarization, proved the existence of pitting corrosion at this pH.

Synthesis, crystal structure, magnetic properties and 57Fe Mossbauer spectroscopy of the new trinuclear [Fe3(4-(2'-hydroxyethyl)-1,2,4- triazole)6(H2O)6](CF3SO3)6 spin crossover compound

Hyetrz = 4-(2prime-hydroxyethyl)-1,2,4-triazole represents the first structurally characterized iron(II) spin crossover compound for which the structure has been solved above and below room temperature in both spin states. The compound crystallizes in the trigonal system, space group R3, a = 12.763(1) b= 67.144(1), V = 1684.3(1) 3, Z = 6 at 120K. At 330K the space group is retained and a = 13.0183(3) b=67.376(3), V = 1805.8(1) 3. The molecular structure consists of trinuclear FeII entities linked together by an unprecedented three-dimensional network of hydrogen bonds. This compound shows a gradual spin crossover behavior centered around room temperature, which has been followed by temperat…

Changes of lead silicate glasses induced by leaching

Abstract The structural differences in the surface region between freshly fractured and leached silicate glasses containing 16.7, 18.8 and 44.4 mol% PbO, respectively, were investigated by photoelectron spectroscopy (XPS). The optical properties and the thicknesses of leached layers were determined by reflection measurements. The binding energies of the O1s signal components for untreated samples can be ascribed to non-bridging (NBO) and bridging (BO) oxygen and oxygen associated with lead as network former (OPb). The binding energy of OPb was found to be 529.1 ± 0.2 eV. For quantitative conclusions, relative XPS sensitivity factors were determined for oxygen, silicon and lead in these glas…

Chemical Applications of Mössbauer Spectroscopy

The Tutorial Lecture begins with a brief recapitulation of the hyperfine interactions and the relevant parameters observable in a Mossbauer spectrum. The main chapter with selected examples of chemical applications of Mossbauer spectroscopy follows and is subdivided into sections on: basic information on structure and bonding; switchable molecules (thermal spin transition in mono- and oligonuclear coordination compounds, light-induced spin transition, nuclear-decay-induced spin transition, spin transition in metallomesogens); mixed-valency in biferrocenes and other iron coordination compounds, and in an europium intermetallic compound; electron transfer in Prussian blue-analog complexes; mo…

LIESST Effect in Fe(II) 1,2,4-Triazole Chains

One-dimensional Fe(II) chains with 1,2,4-triazole as bridging ligands present the LIESST effect; i.e. their spin state switched from low-spin to high-spin after light irradiation at low temperature. This account summarizes the findings in this area of photomagnetism where 57Fe Mossbauer spectroscopy was used as a primary detection tool of the LIESST effect.

Synthesis, Structure, and Magnetic Properties of a Tris[3-(2-pyridyl)-1,2,4-triazole]iron(II) Spin-Crossover Complex

The synthesis and characterization of tris[3-(pyridin-2-yl)-1,2,4-triazole]iron(II) bis(tetrafluoroborate), obtained from the reaction of 3-(pyridin-2-yl)-1,2,4-triazole (Hpt) and hexaaquairon(II) tetrafluoroborate, [Fe(H2O)6](BF4)2, is described, together with its crystal structures at two temperatures. X-ray crystallographic parameters are as follows: [Fe(Hpt)3](BF4)2·nH2O (n ≈ 2) at 250 K: orthorhombic space group Pbam, a = 15.8068(18) A, b = 17.2800(14) A, c = 21.215(2) A, V = 5794.7(10) A3, and Z = 8. [Fe(Hpt)3](BF4)2·nH2O (n ≈ 2) at 95 K: orthorhombic space group Pbam, a = 15.7080(12) A, b = 17.1023(16) A, c = 21.006(2) A, V = 5643.1(9) A3, and Z = 8. The FeII ions are (at both temper…

Conversion electron Mössbauer study of vacuum and thermally treated vivianite

Natural vivianite samples were studied by Mossbauer transmission and conversion electron spectroscopy. The intensities of ferrous doublets in vivianite and the widths of the resonance lines depend strongly on the origin of the samples, on their preparation history, and on exposures in vacuo as well as on thermal treatments. An additional ferrous doublet appearing in samples after vacuum treatment can be ascribed to a tetrahydrate phosphate phase appearing at the surface due to dehydration. Heating at 413 K in dry air for periods of 15–240 min causes a higher oxidation and decomposition rate at the surface region than in the bulk of vivianite. All results do not confirm the assumption publis…

Quadrupole splitting of Fe(II) spin crossover compounds study of temperature and pressure dependence and the implication for the interaction mechanism

The temperature and pressure dependence of the quadrupole splitting ΔE Q of the 3/2→1/2 nuclear Mossbauer transition of57Fe in the spin crossover compounds [Fe x Zn1−x (2-pic)3]Cl2⋆EtOH and the deuterated analog [Fe x Zn1−x (2-pic-ND2)3] Cl2⋆EtOD (2-pic=2-picolylamine) have been studied. The change of ΔE Q can be linearly related to the defomation of the lattice as observed by X-ray measurements. The dependence of ΔE Q on temperatureT, pressurep, and the fraction γ of molecules in the electronic high spin state in the pure iron (x=1) compounds is therefore interpreted as a result of the change of the lattice contribution to the electric field gradient (EFG) at the nucleus only. The intrinsi…

Synthesis, Structure and Properties of a Mixed Mononuclear/Dinuclear Iron(II) Spin-Crossover Compound with the Ligand 4-(p-Tolyl)-1,2,4-triazole

A new iron(II) compound with the formula [Fe2(L)5(NCS)4]2[Fe(L)2(NCS)2(H2O)2] (I) [where L = 4-(p-tolyl)-1,2,4-triazole] has been synthesized and subjected to X-ray structure determination. Compound I crystallizes in the triclinic space group P–1 (no. 2) with a = 14.5785(11), b = 16.1253(11), c = 16.1963(8) A, α = 80.930(5), β = 85.796(5), γ = 78.132(6)°, V = 3676.2(4) A3. The structure refinement converged to wR2 = 0.172, RF = 0.084. The structure was found to consist of two types of iron-containing structural units, a mononuclear unit and a dinuclear one. The mononuclear unit has a crystallographic inversion centre, and is coordinated by two NCS anions, two triazole N1 nitrogen atoms, and…

A spin transition molecular material with a wide bistability domain.

International audience; [Fe(hyptrz)3](4-chloro-3-nitrophenylsulfonate)22 H2O (1; hyptrz=4-(3-hydroxypropyl)-1,2,4-triazole) has been synthesized and its physical properties have been investigated by several physical techniques including magnetic susceptibility measurements, calorimetry, and Mössbauer, optical, and EXAFS spectroscopy. Compound 1 exhibits a spin transition below room temperature, together with a very wide thermal hysteresis of about 50 K. This represents the widest hysteresis loop ever observed for an FeII-1,2,4-triazole spin transition material. The cooperativity is discussed on the basis of temperature-dependent EXAFS studies and of the structural features of a CuII analogu…

Nature of the phase transition in spin crossover compounds

Abstract Starting from the phenomenological free energy describing the spin equilibrium of continuous or gradual high spin (HS) ⇌ low spin (LS) transitions a reduced equation of state has been derived which is of the type known in mean field theories. The continuous HS ⇌ LS transitions of [Fe(2-pic-ND 2 ) 3 ]Cl 2 ·EtOD (2-pic = 2-picolylamine) at ambient pressure and p = 1200 bar and of [Fe(2-pic) 3 ]Cl 2 -MeOH can be classified as isobars above the critical point of the system. Around and below the critical point a complex behaviour is expected for thermodynamic reasons combined with the consequences of an elastic interaction mechanism between the HS and LS complex molecules in the crystal…

Spin Crossover Phenomenon in Nanocrystals and Nanoparticles of [Fe(3-Fpy)2M(CN)4] (MII = Ni, Pd, Pt) Two-Dimensional Coordination Polymers

The two-dimensional spin crossover (SCO) polymers [Fe(3-Fpy)2M(CN)4] (MII = Ni(1), Pd(2), Pt(3)) were nanostructured in the form of nanocrystals and nanoparticles, and their chemical, structural, and physical characterization was carried out using different experimental methods (powder X-ray diffraction, magnetic susceptibility measurements, Mossbauer and infrared spectroscopy, transmission and scanning electronic microscopy, etc.). Surfactant-free nanocrystals of average dimensions 400 × 400 × 30 nm (1a, 1a*, 2a, 3a) were synthesized from water in oil microemulsions (w/o) while nanoparticles of average size 200 × 100, 100 × 60, and 70 × 30 nm were obtained in poly(vinylpyrrolidone) (PVP) c…

Metastable electronic states induced by nuclear decay and light

Radioactive atoms incorporated in insulating solid-state compounds create various kinds of chemical and physical “after-effects” upon nuclear disintegration. Mossbauer emission spectroscopy of57Co-labelled coordination compounds has undoubtedly become the most informative technique to detect such after-effects like aliovalent charge and spin states of the nucleogenic iron atom resulting from the57Co(EC)57Fe decay, low energy excitations of crystal field and Zeeman states, linkage isomerism, radical formation with subsequent redox reactions, and others. We have extensively studied57Co-labelled complexes with [CoIIN6] cores employing time-integral and time-resolved Mossbauer emission spectros…

Jarosite and hematite at Meridiani Planum from Opportunity's Mossbauer Spectrometer.

Mössbauer spectra measured by the Opportunity rover revealed four mineralogical components in Meridiani Planum at Eagle crater: jarosite- and hematite-rich outcrop, hematite-rich soil, olivine-bearing basaltic soil, and a pyroxene-bearing basaltic rock (Bounce rock). Spherules, interpreted to be concretions, are hematite-rich and dispersed throughout the outcrop. Hematitic soils both within and outside Eagle crater are dominated by spherules and their fragments. Olivine-bearing basaltic soil is present throughout the region. Bounce rock is probably an impact erratic. Because jarosite is a hydroxide sulfate mineral, its presence at Meridiani Planum is mineralogical evidence for aqueous proc…

Electrochemical and conversion electron mössbauer study of corrosion induced by acid rain

Abstract The passivation of low carbon steel was studied in aqueous solution of 0.5M Na2SO4 +0.001M NaHSO3 (pH 3.5, 6.5 and 8.5) which can be considered as a model of acid rain. The used conversion electron Mossbauer spectroscopy (CEMS) with the complementary electrochemical investigations proved that the sulfite ions induce pitting corrosion at pH 3.5 and 6 5 while the measurements showed much weaker pitting at pH 8.5. The compositions and thicknesses of the passive films formed during the electrochemical treatments are determined from the CEM spectra. Only γ-FeOOH was found on the surface of the samples at pH 6.5 and 8.5. Nevertheless, at pH 3.5 the sextet belonging to Fe3C appears in the…

Spin- and phase transition in the spin crossover complex [Fe(ptz)6](BF4)2 studied by nuclear inelastic scattering of synchrotron radiation and by DFT calculations

Abstract Nuclear inelastic scattering (NIS) spectra of [Fe(ptz) 6 ](BF 4 ) 2 (ptz = 1- n -propyl-tetrazole) have been measured for five phases differing in spin state and crystallographic structure. Different spectral patterns have been found for the low-spin and high-spin phases and are described in terms of normal coordinate analysis of the complex molecule. For both low-spin and high-spin phases the conversion from ordered to disordered phase results in splitting of the observed NIS bands. Packing becomes visible in the NIS spectra via coupling of the Fe–N stretching vibrations with those of the terminal n -propyl groups. The DFT-based normal coordinate analysis also reveals the characte…

Spin Transitions in Iron(II) Complexes

Iron(II) has the 3d6 outer electronic configuration and hence its octahedral complexes may be either high-spin or low-spin. The high-spin configuration, t 2g 4 e g 2 , is adopted when relatively weak-field ligands are coordinated while the low-spin, t 2g 6 e g 0 , is obtained when strong-field ligands are involved. In Oh symmetry the ground states are 5T2g and lA1g, for the high-spin and low-spin configurations, respectively. While in most iron(II) six-coordinate complexes the symmetry is lower than Oh, these designations are generally adopted in the following sections for convenience. [Fe(H2O)6]2+ and [Fe(en)3]2+ (en = ethylenediamine) are typical examples of high-spin complexes, while [Fe…

Muon spin relaxation studies of iron(II) spin crossover complexes

A series of model iron(II) spin crossover complexes have been investigated by temperature dependent muon spin relaxation (mu SR) techniques at ISIS, UK. The thermally induced spin crossover in these materials could be monitored by following the initial asymmetry parameter, a(0), in zero-field. We established that the behavior of a(0) correlates well with the shape of the spin crossover curve derived from magnetic susceptibility measurements, whether hysteretic, smooth, or abrupt. In addition, the longitudinal field dependence of a(0) not only provides information on the nature of the muonic species but also on their interactions and respective localization in the crystal lattice. Useful ins…

Positron annihilation study of spin-crossover in [Fe x Zn1−x (ptz)6](BF4)2 single crystals

Positron lifetime measurements were carried out on [Fe x Zn1−x (ptz)6](BF4)2 single crystals in the temperature range of 72–300 K. Complementary Doppler broadening spectra were also recorded at room temperature. The probability of the formation of o-Ps (lifetime 500–1400 ps) was between 10–30%. Both the spin density and the lattice parameters of the sample affected the lifetime of o-Ps through the ortho-para conversion and the pick-off annihilation, respectively. The positron annihilation technique proved to be a sensitive detector of the spin-crossover5T2 ↔1A1 and of the concomitant phase transformation.

Anomalous Spin Transition Observed in Bis(2,6-bis(pyrazol-3-yl)pyridine)iron(II) Thiocyanate Dihydrate

Bis(2,6-bis(pyrazol-3-yl)pyridine)iron(II) thiocyanate dihydrate undergoes a two-step singlet (1A1) ⇄ quintet (5T2) transition in which both steps are associated with thermal hysteresis. Thermal cycling of the sample results in its conversion to a second phase which displays a single-step transition with a very narrow hysteresis loop. This second phase slowly reverts to the initial phase on standing at 300 K. The interconversions are completely reversible. The spin state changes have been monitored by measurement of magnetism and Mossbauer spectra and by differential scanning calorimetry (DSC) studies.

Stoichiometry of LiNiO2 Studied by Mössbauer Spectroscopy

From the 61Ni and 57Fe Mossbauer spectroscopy data follows the cationic site assignment in Li1−x Ni1+x O2. Our data explain the ferromagnetic properties of this material because of the appearance of Ni2+ (S = 1) among Ni3+ (S = 1/2) in Ni3+O2 hexagonal planes. We have no evidence for the ferromagnetic interaction between the NiO2 layers through the excess Ni2+ ions substituting the Li+ ions. The presence of Ni2+ found in the Ni3+O2 planes explains the absence of the Jahn-Teller distortions probably because of the electronic transfer between the Ni3+ and Ni2+ ions.

Titelbild: Mixed Spin-State [HS-LS] Pairs in a Dinuclear Spin-Transition Complex: Confirmation by Variable-Temperature57Fe Mössbauer Spectroscopy (Angew. Chem. 16/2008)

Photomagnetic properties of an Iron(II) low-spin complex with an unusually long-lived metastable LIESST state

A comprehensive study of the photomagnetic behavior of the [Fe(L222N5)(CN)2].H2O complex has been carried out. This complex is characterized by a low-spin (LS) iron(II)-metal center up to 400 K and exhibits at 10 K the well-known Light-Induced Excited Spin State Trapping (LIESST) effect. The critical LIESST temperature (T(LIESST)) has been measured to be 105 K. The kinetics of the transition from the metastable high-spin (HS) state to the low-spin state have been determined and used for reproducing the experimental T(LIESST) curve. This study represents a second example of a fully low-spin iron(II)-metal complex up to 400 K, which can be photoexcited at low temperature with an atypical long…

Thermal and optical switching of bistable iron compounds and possible applications

Abstract Iron(II) coordination compounds with ligand field strengths close to the mean spin pairing energy may undergo thermal spin transition in the solid as well as in the liquid state. The thermodynamically stable state is high spin (HS) 5T2 (under Oh symmetry) with (t2)4 e2 electron configuration above the critical transition temperature Tc, and low spin (LS) 1A1 with (t2)6 electron configuration below Tc. The spin transition curve γHS(T) (molar fraction of HS molecules as function of temperature) can be abrupt or gradual, with or without hysteresis, or even with a plateau near Tc. Tc itself can vary over the whole temperature scale between the liquid helium region up to above room temp…

Mössbauer effect study of the electronic ground state of iron(II)in tris(2-chlorophenanthroline)iron(II) perchlorate

Abstract Mossbauer spectra of [Fe(2-Cl-phen) 3 ](ClO 4 ) 2 ·H 2 O have been measured in the temperature range 293 − 5 K. The spectra indicate that the iron atom in this compound possesses a spin quintet ground state throughout the temperature range under study, in contradiction to the suggested high spin-low spin transition, which has been concluded from a magnetic susceptibility study by other authors. From a theoretical analysis of the temperature dependence of the quadrupole splitting, with trigonal distortion, spin-orbit coupling, and effects of covalency taken into account, the ground term of iron(II) in this compound has been elucidated as being 5 A 1 ( 5 T 2g ), separated from the 5 …

Effect of the metal dilution on the thermal and light-induced spin transition in [FexMn1−x(bpp)2](NCSe)2: When T(LIESST) reaches T1/2

International audience; The thermal and light-induced spin transition in [FexMn1−x(bpp)2](NCSe)2 (bpp = 2,6-bis(pyrazol-3-yl)pyridine) has been investigated by magnetic susceptibility, photomagnetism and diffuse reflectivity measurements. These complexes display a thermal spin transition and exhibit the light-induced excited spin state trapping (LIESST) effect at low temperature. For each mixed-crystal system, the thermal spin transition temperature, T1/2, and the relaxation temperature of the photo-induced high-spin state, T(LIESST), have been systematically determined. It appears that T1/2 decreases with the metal dilution while T(LIESST) remains unchanged, suggesting that the two interco…

Application of 61Ni Mössbauer spectroscopy to chemical problems

Using the possibility to produce 61Co sources at the MAinz MIcrotron, 61Ni Mossbauer spectroscopy was applied to different kinds of chemical problems. Measurements of isomer shifts and V zz values in some common compounds and compounds with unusual chemical bonding for comparison with band structure calculations, measurement of 61Ni Mossbauer parameters in model compounds for hydrogenase and dehydrogenase with an active [NiS4] centre, and study of novel binary NiF3 compounds at helium temperature are presented.

Mössbauer effect study of the temperature and pressure dependence of the singlet-quintet intersystem crossing dynamics in an iron(II) spin crossover complex

The lineshapes of Mossbauer spectra of the iron(II) spin crossover complex [Fe(6-mepy)3 tren] (PF6)2 are affected by the dynamics of the HS⇌LS equilibrium. The lineshapes are reproduced with a stochastic two-state-relaxation-model yielding rate constants similar to those determined for related complexes in solution. Application of an external pressure of 150 MPa increases the relaxation rate.

Pressure-induced electron transfer in ferrimagnetic Prussian blue analogs

M\"ossbauer and magnetic susceptibility measurements were performed under pressure on three Prussian blue analogs, ${\mathrm{K}}_{0.1}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.7}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O},$ ${\mathrm{K}}_{0.28}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.76}\ensuremath{\cdot}18{\mathrm{H}}_{2}\mathrm{O},$ and ${\mathrm{Cs}}_{0.7}{\mathrm{Co}}_{4}[{\mathrm{Fe}(\mathrm{CN})}_{6}{]}_{2.9}\ensuremath{\cdot}16{\mathrm{H}}_{2}\mathrm{O}.$ A pressure-induced electron transfer ${\mathrm{Co}}^{2+}(S=\frac{3}{2})\ensuremath{-}{\mathrm{Fe}}^{3+}(S=\frac{1}{2})\ensuremath{\rightarrow}{\mathrm{Co}}^{3+}(S=0)\ensuremath{-}{\mathrm{Fe}}^{2+}(S=0)…

X-ray study of the light-induced metastable state of a spin-crossover compound

Iron(II) complexes exhibiting thermal spin crossover may be converted from the1A1low-spin (LS) state to the5T2high-spin (HS) state by irradiation with green light (light-induced excited spin-state trapping, LIESST). The lifetime of the metastable LIESST state may be sufficiently long for X-ray diffraction study. The lattice parameters of a single crystal of [Fe(ptz)6](BF4)2(ptz = propyltetrazole) were measured between 300 and 10 K, while the crystal changed from the HS to the LS state near 135 K. Using the green light (514 nm) of an argon-ion laser, the crystal was quantitatively converted to the metastable LIESST state at 10 K; its lattice parameters were measured up to 50 K, at which poin…

Magnetization and61Ni Mössbauer effect study of the ternary arsenide CrNiAs

The results of x-ray diffraction, dc magnetization, and 61Ni M?ssbauer spectroscopy studies of the ternary arsenide CrNiAs are reported. This compound crystallizes in the orthorhombic Fe2P-type structure (space group ) with the lattice parameters a = 6.1128(2)?? and c = 3.6585(1)??. CrNiAs is a mean-field ferromagnet with Curie temperature TC = 171.9(1)?K and the critical exponents ? = 0.514(18), ? = 1.010(16), and ? = 2.922(10). The temperature dependence of the magnetic susceptibility above TC follows the modified Curie?Weiss law with a paramagnetic Curie temperature of 176.0(3)?K and effective magnetic moment per transition metal atom of 2.42(1)??B. The magnetic moment per formula unit a…

Untersuchungen zur Reaktion von konzentrierter Phosphors�ure mit reinen und korrodierten Stahloberfl�chen

Mittels Mosbauerspektroskopie wurde gefunden, das sich aus Rostkomponenten neben den normalen Eisen (III)- und Eisen (II)-phosphaten auch ein saures Eisen (III)-phosphat bilden kann, wenn sie mit konzentrierter Phosphorsaure behandelt werden. Voraussetzung hierfur ist, das die Ausgangsphase eine reine Fe3+-Verbindung ist. Das saure Eisen(III)-phosphat, wahrscheinlich FeH3(PO4)2 · 2,5 H2O, enthalt Fe3+ in nahezu kubischer Umgebung, die Kristallstruktur hat jedoch niedrigere Symmetrie. Unterhalb von 28 K setzt eine magnetische Ordnung ein. Es sind zwei Falle mit verschiedener Spinstruktur und Verkantungen zu unterscheiden.

Ni participation in the magnetism of Fe-Ni-Si-B amorphous alloys.

$^{61}\mathrm{Ni}$ M\"ossbauer measurements at 4.2 K have been performed on (${\mathrm{Fe}}_{\mathrm{x}}$${\mathrm{Ni}}_{1\mathrm{\ensuremath{-}}\mathrm{x}}$${)}_{77}$${\mathrm{Si}}_{1013}$ amorphous alloys with x=0.0, 0.1, and 0.9. Ni atoms in ${\mathrm{Ni}}_{77}$${\mathrm{Si}}_{10}$${\mathrm{B}}_{13}$ bear no magnetic moment, whereas in (${\mathrm{Fe}}_{0.1}$${\mathrm{Ni}}_{0.9}$${)}_{77}$${\mathrm{Si}}_{10}$${\mathrm{B}}_{13}$ and (${\mathrm{Fe}}_{0.9}$${\mathrm{Ni}}_{0.1}$${)}_{77}$${\mathrm{Si}}_{10}$${\mathrm{B}}_{13}$ their moments are, respectively 0.38${\ensuremath{\mu}}_{B}$ and 0.65${\ensuremath{\mu}}_{B}$. Our results, together with the literature data, show that Ni atoms in Fe-…

Photoswitchable coordination compounds

Photoswitchable compounds represent an attractive class of materials in coordination chemistry. Recent progress dealing with transition metal compounds involving photo-induced changes of the magnetic and/or optical properties to long-lived metastable states are covered in the present review article. The basic photophysical phenomena together with representative examples such as nitroprusside derivatives, relevant spin crossover complexes, stilbenoid complexes and finally Prussian blue analogues are discussed. Some possible applications regarding energy and information storage are suggested at the end.

Mathematical Evaluation of Mössbauer Spectra

As in many other spectroscopic methods, it is necessary in Mossbauer spectroscopy to determine the positions, intensities or areas of the absorption and emission lines as accurately as possible. In the case of poorly resolved or complex hyperfine spectra due to different chemical species or several lattice sites in the sample it is not possible to evaluate the Mossbauer spectra just by hand. In addition, often one is faced with the problem of taking into account cosine smearing effects (Sec. 4.2), thick absorbers associated with the calculation of the transmission integral (Sec. 3.5), magnetic or electric relaxation (Sec. 6.7), or delayed coincidence Mossbauer measurements (Sec. 3.5), which…

“Supramolecular” Solid-State Chemistry: Interpenetrating Diamond-Type Frameworks of U4+ Ions Linked byS,S′-Bidentate P2S62− Molecular Rods in UP4S12

Inseparably interwoven are three independent polymeric diamond-type U(P2 S6 )2 frameworks in the structure of the title compound. The linear P2 S6 units act as molecular rods linking the pseudotetrahedral U4+ centers. U(P2 S6 )2 may be viewed as a coordination polymer which is formed from U/P/S melts by the solid-state equivalent of the self-assembly reactions in solution.

Investigations on the photoelectron conversion efficiency of NaI(Tl) counters

Abstract The photoelectron conversion efficiency of NaI(Tl) detectors has been measured by counting single photoelectron pulses of the detector output pulse train on a very fast storage oscilloscope. This result is compared with those obtained by the measurement of the achievable time resolution using the first photoelectron triggering technique.

Mössbauer mineralogy of rock, soil, and dust at Gusev crater, Mars: Spirit's journey through weakly altered olivine basalt on the plains and pervasively altered basalt in the Columbia Hills

The Moessbauer spectrometer on Spirit measured the oxidation state of Fe, identified Fe-bearing phases, and measured relative abundances of Fe among those phases for surface materials on the plains and in the Columbia Hills of Gusev crater. Eight Fe-bearing phases were identified: olivine, pyroxene, ilmenite, magnetite, nanophase ferric oxide (npOx), hematite, goethite, and a Fe(3+)-sulfate. Adirondack basaltic rocks on the plains are nearly unaltered (Fe(3+)/Fe(sub T) Px), and minor npOx and magnetite. Columbia Hills basaltic rocks are nearly unaltered (Peace and Backstay), moderately altered (WoolyPatch, Wishstone, and Keystone), and pervasively altered (e.g., Clovis, Uchben, Watchtower, …

Mononuclear coordination compounds based on a novel chelating triazole ligand: 1-vinyl-3-acetylamino-1,2,4-triazole

The synthesis, X-ray structure, magnetic and spectroscopic properties of new Co(II), Ni(II) and Cu(II) complexes with 1-vinyl-3-acetylamino-1,2,4-triazole (vaat) are reported. The crystal structures of [Ni(vaat)2(H2O)2](NO3)2 and [Cu(vaat)2(H2O)2]Cl2 have been determined by X-ray diffraction. In these mononuclear complexes, the metal ion is surrounded by two water molecules in axial positions and two oxygen and two nitrogen (N4) atoms coming from two trans-oriented chelating vaat molecules. Anions are noncoordinated and are involved in a hydrogen bonding network. The complex cations of [Cu(vaat)2(H2O)2]Cl2 are aligned within chains. In the structure of [Ni(vaat)2(H2O)2](NO3)2 the nitrate an…

Hybrid Molecular Magnets Obtained by Insertion of Decamethylmetallocenium Cations into Layered, Bimetallic Oxalate Complexes: [ZIIICp*2][MIIMIII(ox)3] (ZIII=Co, Fe; MIII=Cr, Fe; MII=Mn, Fe, Co, Cu, Zn; ox=oxalate; Cp*=pentamethylcyclopentadienyl)

A new series of hybrid organometallic - inorganic layered magnets with the formula [Z(III)Cp*2][M(II)M(III)(ox)3] (Z(III) = Co, Fe; M(III) = Cr, Fe; M(II) = Mn, Fe, Co, Cu, Zn; ox = oxalate; Cp* = pentamethylcyclopentadienyl) has been prepared. All of these compounds are isostructural and crystallize in the monoclinic space group C2/m, as found by X-ray structure analysis. Their structure consists of an eclipsed stacking of the bimetallic oxalate-based extended layers separated by layers of organometallic cations. These salts show spontaneous magnetization below To, which corresponds to the presence of ferro-, ferri-, or canted antiferromagnetism. Compounds in which the paramagnetic deca-me…

Nuclear Resonance Scattering Using Synchrotron Radiation (Mössbauer Spectroscopy in the Time Domain)

Conventional Mossbauer spectroscopy (MS) can be considered as “spectroscopy in the energy domain.” It has been widely used since its discovery in 1958 [1]. Nuclear resonant forward scattering (NFS) of synchrotron radiation has been successfully employed as a time-differential technique since 1991 [2]. Another related technique, nuclear inelastic scattering (NIS) of synchrotron radiation [3], can be regarded as an extension of conventional, energy-resolved MS (in the range 10−9 to 10−7 eV) to energies on the order of molecular vibrations (in the range 10−3 to 10−1 eV). So far only a few “Mossbauer” stations for NFS and NIS measurements have become available in synchrotron laboratories, i.e.,…

Spin state switching in iron coordination compounds

The article deals with coordination compounds of iron(II) that may exhibit thermally induced spin transition, known as spin crossover, depending on the nature of the coordinating ligand sphere. Spin transition in such compounds also occurs under pressure and irradiation with light. The spin states involved have different magnetic and optical properties suitable for their detection and characterization. Spin crossover compounds, though known for more than eight decades, have become most attractive in recent years and are extensively studied by chemists and physicists. The switching properties make such materials potential candidates for practical applications in thermal and pressure sensors …

Spin Crossover Systems

Abstract This account constitutes a basic introduction to spin crossover phenomena that is mostly encountered for iron(II) coordination complexes. After briefly describing the occurrence of spin transition in liquid and solid states, the effects of pressure and light irradiation are discussed. Applications and recent trends of this expanding field are also presented.

Spin Transition in Iron Compounds

First-row transition metal complexes with d4 up to d7 electron configuration in octahedral ligand fields (and d8 electron configuration in six-coordinate complexes of lower symmetry) may undergo temperature dependent high spin (HS) ⇌ low spin (LS) transition, provided the ligand field strength (Δ), including low symmetry contributions, becomes comparable in magnitude with the mean spin pairing energy (P). At a critical field strength Δcrit = P, the energy levels of the two spin states cross. This is illustrated in Fig. 1, where a simplified Tanabe-Sugano type energy level diagram for d6 systems (e.g. Fe2+, Co3+) is shown as an example. For weak ligand fields, Δ Δcrit, the LS state1A1g(Oh) b…

57Fe- MÖSSBAUER EMISSION SPECTROSCOPY OF AN IRON (II) COMPLEX WITH TEMPERATURE DEPENDENT SPIN STATE

Spin Crossover in a Supramolecular Fe4II [2×2] Grid Triggered by Temperature, Pressure, and Light

A multiplex electronic switch on the molecular level has been realized by using a tetranuclear FeII complex of the [2×2] grid type. The four metal ions can be switched stepwise between their high-spin and low-spin states by temperature, pressure, and light, thus representing a triple level, triple switch system as illustrated in the picture.

A time-differential Mössbauer emission spectrometer with high efficiency and high time resolution

A high-efficiency, high rate-capability, computer-based measuring setup for Time-Differential Mossbauer Spectroscopy was constructed. Applying NaI(Tl) and plastic scintillators for the detection of the 14.4 keV and 122 keV γ-radiation respectively, a superior timing (2, 3 ns FWHM) was achieved by a “fast-fast-ultra fast” timing method developed for that purpose.

Cover Picture: Mixed Spin-State [HS-LS] Pairs in a Dinuclear Spin-Transition Complex: Confirmation by Variable-Temperature57Fe Mössbauer Spectroscopy (Angew. Chem. Int. Ed. 16/2008)

INVESTlGATlON OF THE SPIN CROSSOVER IN [FexM1-x(Phen)2 (NCS)2] (M = Mn, Co, Ni)

Magnetic Ordering and Spin Dynamics of Ba1-xEuxSi Phases

We have investigated the magnetic ordering and spin dynamics of the solid solution series Ba1–xEuxSi with 0 < x ≤ 1 applying X-ray diffraction, electric conductivity measurements, Mossbauer spectroscopy, muon spin depolarization, and neutron diffraction. Our results suggest a spin glass-like behavior of Ba1–xEuxSi for concentrations close to x = 0.3 exist. Different spin ordering phenomena are found, which are dependent on the relative europium concentrations.

Spin transition in [Fe(phen)2(NCS)2] - �SR study

The reversible thermal spin transition which occurs in [Fe(phen)(2)(NCS)(2)] around T-1/2 similar to 177 K has been investigated by muon spin relaxation (muSR) (similar to10-280 K). The depolarisation curves are well described by two Lorentzian lines represent fast and slow components in the decay curves, with the initial asymmetry parameter of the fast component found to track the spin transition in [Fe(phen)2(NCS),]. Comparison of zero-field and transverse field (20 Oe) muSR measurements shows that diamagnetic muonic species occur over the entire temperature range.

Pressure-Induced High Spin State in [Fe(btr)2(NCS)2]·H2O (btr = 4,4′-bis-1,2,4-triazole)

Application of hydrostatic pressure (≤ 10.5 kbar) on the two-dimensional spin transition compound [Fe(btr)2(NCS)2]·H2O (btr = 4,4‘-bis-1,2,4-triazole) results in an unexpected stabilization of the HS state. On release of the pressure, the HS state is found to be partially trapped. After thermal relaxation of the metastable HS state obtained by the LIESST effect (light-induced excited spin state trapping), a pure LS state is obtained in contrast to the pressure experiments. This different behavior supports a structural phase transition as the likely basis of the pressure-induced HS state.

Mössbauer Emission Spectroscopy of Mixed-Valency after Nuclear Decay in Iron Complexes

The population of anomalous spin states and aliovalent charge states of iron induced by the 57 Co(EC)57 Fe nuclear decay in polycristalline transition metal compounds was studied by means of Coincidence Mossbauer Emission Spectroscopy (CMES), that is Time-Differential Mossbauer Emission Spectroscopy (TDMES) as well as γ/Xray-Coincidence Mossbauer Emission Spectroscopy (γ/X-CMES). By use of time-integral Mossbauer emission spectroscopy (TIMES) we have observed anomalous high spin (S = 2) states of 57 Fe(II) in the system [57Co/Co(phen)3(ClO 4)2 with increasing intensities on lowering the temperature. With TDMES we followed quantitatively the high spin-low spin relaxation kinetics in this com…

Mössbauer Spectroscopy: Elegance and versatility in chemical diagnostics

Dedicated to Professor Rudolf Ludwig Mossbauer on the occasion of his 80th birthday . Soon after the discovery of the recoilless nuclear resonance fluorescence by Rudolf L. Mossbauer some fifty years ago a new spectroscopic technique developed quickly on the basis of this resonance phenomenon as an excellent tool for the investigation of materials through electric and magnetic hyperfine interactions between electrons and suitable Mo uml ssbauer nu-clides. Many disciplines of solid state research have benefited from applications of the new tool for non-destructive phase analysis. Chemists in particular have recognized the information that can be derived from Mo uml ssbauer spectra regarding …

AES and CEMS analysis of the formation of layers on Si steel under thermal treatment in a flux of H2/water vapour

The near surface diffusion and reaction processes in iron-silicon steel (3.1 wt.%Si) during 10 min decarburization in water vapour/hydrogen have been studied. The decarburization temperature has been varied between 506 and 714°C for the fixed partial pressure ratio pH2O/pH2=0.017. An outer layer of SiO2 forms on the surface with its thickness increasing with temperature. From 600°C upwards, the decarburization process is hindered and a cementite layer is formed below the SiO2 layer. The formation of fayalite at the surface has been studied at a fixed decarburization temperature with pH2O/pH2 ranging from 0.017 to 0.49. The scale thickness reduces abruptly just before the ratio pH2O/pH2 nece…

Spin Transition Phenomena

Direct monitoring of spin state in dinuclear iron(II) coordination compounds

So far there has been no direct method to determine the spin state of molecules in dinuclear iron(II) compounds. The molecular fractions of high-spin (HS) and low-spin (LS) species have been deduced from magnetic susceptibility and zero-field Mossbauer spectroscopy data irrespective of whether they belong to LS–LS, LS–HS and HS–HS pairs. However, the distinction of pairs becomes possible if Mossbauer measurements are carried out in an external magnetic field. The proposed method opens new possibilities in the study of spin crossover phenomena in dinuclear compounds.

Heat-capacity anomaly due to spin reorientation and thermodynamic functions of ErFeO3 and TmFeO3

Abstract Heat capacities of orthoferrites, ErFeO 3 and TmFeO 3 , have been measured below room temperature by adiabatic calorimetry. A broad but definite anomaly due to the spin reorientation phenomenon was successfully detected in the expected temperature range (ca. 90 K). The results are compared with a vast anomaly reported for YbFeO 3 . The temperature dependence of the electric quadrupole splitting of the Fe nuclear levels was determined by Mossbauer spectroscopy through the spin reorientation. A heat capacity anomaly centered at 3.60 K due to the magnetic ordering of Er 3+ ions was clearly detected. Some Schottky anomalies were resolved and energy splittings involved were roughly esti…

A CEMS/AES study of the passivation of iron

The passivation of iron and steel (DIN 1623) was studied by integral and depth selective conversion electron Mossbauer spectroscopy and Auger electron spectroscopy. Thickness and phase composition of the passive layer formed in sulphate solution and in a phosphate buffer were determined in dependence on the anodic potential and the duration of the passivating procedure. The experimental results lead to the conclusion that not the whole oxidic layer is responsible for the passivity but only a very thin intermediate layer formed between the cubic substrate and the rhombic oxide (γ-FeOOH) cover.

Spin crossover star-shaped metallomesogens of iron(II).

Three new types of spin crossover (SCO) metallomesogens of Fe-II based on symmetric tripod ligands and their magnetic and structural properties are reported here. These were obtained by condensation of tris(2-aminoethyl)-amin (tren) with the aldehyde derived from 3-alkoxy-6-methylpyridine (mpyN, N (number of carbon atoms in n-alkyl chains) = 8, 18), 1-alkyl-1H-imidazole (imN, N = 4, 16, 18, 20, 22), or 1-alkyl-1H-benzimidazole (bimN, N = 6, 14, 16, 18, 20). A complex derived from 1-octadecyl-1H-naphtho[2,3-d]imidazole (nim18) retains the high spin state at any temperature. Single crystals of the short-chain complexes were investigated by a combination of X-ray crystallography, magnetic meas…

Coexistence of spin-crossover and antiferromagnetic coupling phenomena in the novel dinuclear Fe(II) complex [Fe(dpa)(NCS)2]2bpym

Abstract The iron(II) spin crossover dinuclear compound [Fe(dpa)(NCS) 2 ] 2 bpym where dpa = 2,2 ′ -dipyridylamine and bpym = 2,2 ′ -bipyrimidine has been synthesized and characterized. Variable-temperature magnetic susceptibility and 57 Fe Mossbauer spectroscopy data provide evidence for a rather complete and continuous S=2 ( HS )↔S=0 (LS) spin-crossover behavior taking place in the temperature range 400–50 K (T 1/2 =245 K ) without the presence of a plateau at 50% of conversion. The absence of such plateau, which is characteristic of all dinuclear compounds so far studied, is interpreted in terms of synergetic effect between intramolecular and intermolecular interactions.

Crystal‐Structure Studies of Mononuclear Iron(II) Complexes with Two‐Step Spin Crossover: [Fe{5‐NO 2 ‐sal‐N(1,4,7,10)}] Revisited

In the region of the spin transition of spin-crossover (SCO) compounds there coexist molecules in both high-spin (HS) and low-spin (LS) states. In the case of two-step spin transition, theoretical predictions and computer simulations have shown that HS and LS complex molecules should be ordered in the plateau region. Several examples that support this hypothesis are already presented in the literature. Herein, we discuss a mononuclear complex of iron(II) with two-step spin transition in terms of long-range ordering of HS and LS molecules. In such compounds, spin transition is associated with the formation of a superstructure. However, previous studies of the [Fe{5-NO2-sal-N(1,4,7,10)}] [5-N…

Spin crossover in iron(II)-complexes

The effect of low pressure on a high-spin—low-spin transition

Abstract The effect of low pressure ( p = 150 bar) on the high-spin (HS)—low-spin (LS) transition in [Fe x Zn 1− x (2-pic) 3 ]Cl 2 · EtOH ( x = 0.5, 1.0) was measured by Mossbauer spectroscopy and the results compared with theory. The linear dependence of the volume of the lattice on the HS fraction, which is the basic assumption of the theory, was proven by temperature dependent X-ray measurements.

Polymorphism and Pressure Driven Thermal Spin Crossover Phenomenon in [Fe(abpt)2(NCX)2] (X=S, and Se): Synthesis,Structure and Magnetic Properties

The monomeric compounds [Fe(abpt 2(NCX)2(X = S (1), Se (2) and abpt = 4-amino- 3,5-bis(pyridin-2-yl)-1,2,4-triazole) have been synthesized and characterized. They crystallize in the monoclinic P21/n space group with a = 11.637(2) A, b = 9.8021(14) A, c = 12.9838(12) A, β = 101.126(14)°, and Z=2 for 1, and a= 11.601(2) A, b = 9.6666(14) A, c = 12.883(2) A, β = 101.449(10)°, and Z = 2 for 2. The unit cell contains a pair mononuclear [Fe(abpt)2(NCX)21 units related by a center of symmetry. Each iron atom, located at a molecular inversion center, is in a distorted octahedral environment. Four of the six nitrogen atoms coordinated to the Fe(II) ion belong to the pyridine-N(1) and triazole-N(2) r…

Influence of Metal Dilution on the Light‐Induced Spin Transition in Two 1D Chain Compounds: [Fe x Zn 1– x (btzp) 3 ](BF 4 ) 2 and [Fe x Zn 1– x (endi) 3 ](BF 4 ) 2 {btzp = 1,2‐Bis(tetrazol‐1‐yl)propane and endi = 1,2‐Bis(tetrazol‐1‐yl)ethane}

The thermal and light-induced spin transitions in [FexZn1–x(btzp)3](BF4)2 and [FexZn1–x(endi)3](BF4)2 {btzp = 1,2-bis(tetrazol-1-yl)propane; endi = 1,2-bis(tetrazol-1-yl)ethane} chain compounds have been investigated by magnetic susceptibility, photomagnetism and diffuse reflectivity measurements. These compounds display a thermal spin transition and the Light-Induced Excited Spin State Trapping (LIESST) effect at low temperature. For each compound, the thermal spin transition temperature, T1/2, and the relaxation temperature of the photo-induced high-spin state, T(LIESST), have been systematically determined. A decrease in T1/2 induces an increase in T(LIESST). The results are discussed an…

Phasenumwandlungen in Korrosionsschichten auf Eisen: Mößbauerspektroskopische Untersuchungen

Zur Untersuchung der Korrosion von Stahlblechen wurde die mosbauerspektroskopische Phasenanalyse in Transmissions- und Streugeometrie eingesetzt. Die Korrosion von Stahlblechen fuhrt in einer Atmosphare von geringer Korrosivitat nach langen Expositionszeiten vorwiegend zu den relativ stabilen β-Phasen der moglichen Fe-Korrosionsprodukte. Bei durch HCl-Zusatz erhohter Korrosivitat ergibt sich eine Bevorzugung der Bildung von β-FeOOH und kein Auftreten der α-Phasen. Auch der Einflus von. Beschichtungen auf die Phasenzusammensetzung wird behandelt. Die Entstehung und Umwandlung der verschiedenen Fe-haltigen Phasen im Rost last sich anhand eines Stabilitatsdiagramms verstehen. Auch die Wirkung …

Iron(II) Spin Transition Complexes with Dendritic Ligands, Part I

The ligands G1- and G2-oligo (benzyl ether) (PBE) dendrons and their iron(II) complexes [Fe(Gn-PBE)3]A2·xH2O (with n = 1, 2 and A = triflate, tosylate) were prepared. The magnetic properties of the complexes were investigated by a SQUID magnetometer. All complexes exhibit gradual spin transition below room temperature. At very low temperatures the magnetic behaviour reflects zero-field splitting (ZFS) effects. 57Fe-Mossbauer spectroscopy was performed to distinguish between ZFS of high spin species and spin state conversion into the low spin state. Further characterisation was carried out by thermogravimetric analysis (TGA) and FT-IR spectroscopy. Structural features have been determined by…

Quantitative determination of fayalite layers on iron by CEMS

In the processing of silicon iron (Fe-3%) Si), so-called ‘fayalite layers’ are formed. By CEMS, they were found to consist of an outer Fe3+-oxide layer and an inner Fe2SiO4 (fayalite) layer. Sometimes an additional wustite contribution was found. Thef-factor of fayalite was determined experimentally (ffayalite/fα-Fe=0.47±0.04) and, by use of it, the thicknesses of the layers on some silicon iron samples could be calculated from CEMS data.

Pressure induced increase in Tc for the organic-based magnet FeII(TCNE)2 (TCNE=tetracyanoethylene)

Abstract Pressure dependent magnetization and 57Fe Mossbauer studies were performed on Fe(TCNE)[C4(CN)8]1/2·zCH2Cl2 (TCNE = tetracyanoethylene). Pressure did not influence the Mossbauer parameters in paramagnetic state. Mossbauer data reveals the onset of magnetic ordering at 130 K and significant enhancement of the magnetic ordering temperature from 100 to 150 K accompanied by an increase of the spontaneous magnetization, which is higher than reported from the magnetic data, and application of pressure induces the reversible formation of a new, metastable magnetic species. These changes suggest an increase of the dimensionality of magnetic interaction, i.e., stronger interlayer coupling. A…

Spin crossover in iron(II) complexes: Recent advances

In this review article, several representative multifunctional SCO materials exhibiting interplay/synergy between the spin transition and magnetic coupling or liquid crystalline properties together with the present pioneering works on nano-structuration of SCO materials are illustrated. As the Mossbauer spectroscopy has been decisive in the study of the physical properties of these multifunctional materials, special attention is given to their corresponding Mossbauer investigations.

Synthesis, X-ray structure and magnetic properties of the azido adducts of quadridentate Schiff base manganese(III) complexes

Abstract Two new azido derivatives of quadridentate Schiff base manganese(III) complexes have been synthesized and characterized structurally and magnetically. X-ray structure analysis revealed that both complexes viz. [Mn2(L1)2(N3)2] (1) and [Mn2(L2)2(N3)2] (2), where H2L1=N,N′-(1,1-dimethylethylene)-bis-(salicylaldiimine) and H2L2=bis(o-hydroxyacetophenone)-ethylenediimine exist as phenoxo-bridged dimer. The magnetic susceptibility of the complexes has been measured in the 5–300 K range. At room temperature the MnIII ions in complexes 1 and 2 possess an S=4 ground state. The global magnetic interaction in complex 1 is found to be ferromagnetic, while for complex 2 it is anti-ferromagnetic.

Mononuclear Complexes of Iron(II) Based on Symmetrical Tripodand Ligands: Novel Parent Systems for the Development of New Spin Crossover Metallomesogens

The synthesis and characterization of a series of mononuclear tripodand-based FeII complexes by means of Mossbauer andUV/Vis spectroscopic as well as magnetic methods is reported. The complexes were obtained from the reactions of FeII salt with heterocyclic aldehydes (imd = imidazole-4(5)-carboxaldehyde, py = picolinaldehyde, or 6-Mepy = 6-methylpicolinaldehyde) and a symmetric triamine [tren = tris(2-aminoethyl)amine, tame = 2,2,2-tris(aminomethyl)ethane, or tach = 1,3,5-cis,cis-cyclohexanetriamin]. Because of extreme rigidity of the capping triamine tach, the molecular structure of {Fe[tach(imd)3](BF4)2} (1) features an unprecedented tapered trigonal prismatic FeN6 polyhedron. The molecul…

Exchange-coupled Fe-X-Fe model compounds for certain iron proteins

X-ray structure studies, Mossbauer experiments and magnetic susceptibility measurements were used in connection with molecular orbital calculations to monitor structurally induced changes of electronic and magnetic properties in exchangecoupled [Fe2S2 (SR)4]2- and [Fe2OCl6]2- anions.

Synthesis, crystal structure and magnetic properties of the spin crossover system [Fe(pq)3]2+

Abstract Three new compounds formulated (ClO4)2[Fe(pq)3] (1), (BF4)2[Fe(pq)3] · EtOH (2) and {(ClO4)[MnCr(C2O4)3][Fe(pq)2(H2O)2]} (3), where pq is 2,2′-pyridylquinoline, have been synthesised and characterised. Despite the different crystal packing exhibited by 1 and 2, the cationic species [Fe(pq)3]2+ are structurally quite similar. At 293 K, the Fe–N bond lengths are characteristic of the iron(II) in the high-spin state. In contrast to 1, 2 undergoes a continuous spin transition. Indeed, at 95 K its structure experiences a noticeable change in the Fe–N bonds and angles, i.e. the Fe–N bonds shorten by 0.194 A on the average. The magnetic behaviour confirms that 1 is fully high-spin in the …

Substituent effects on the spin equilibrium in iron(II) pyrazolylborate complexes

Abstract Two new complexes of the iron(II) pyrazolylborate system, [Fe(HB(pz)(dmpz) 2 ) 2 ] and [Fe(HB(pz) 2 (dmpz)) 2 ] (pz = pyrazole, dmpz = 3,5-dimethylpyrazole), have been prepared and found to exhibit thermal spin crossover in toluene solutions by means of optical spectroscopy and magnetic susceptibility measurements. Comparison with the published magnetic behaviour of the complexes [Fe(HB(dmpz) 3 ) 2 ] and [Fe(HB(pz) 3 ) 2 ] shows that the high spin state is stabilized with an increasing number of methyl substituents.

γ-Fe2O3 nanoparticle in NaY-zeolite matrix: Preparation, characterization, and heterogeneous catalytic epoxidation of olefins

Abstract Nano-sized crystals of maghemite iron oxide (γ-Fe 2 O 3 ) were synthesized onto the surface of NaY-zeolite crystals by immobilizing a polynuclear iron complex [Fe 4 O 2 (O 2 CCH 3 ) 7 (bpy) 2 ](ClO 4 ) (bpy = 2,2′-bipyridine) and subsequent calcination of the material in oxygen. Superparamagnetic γ-Fe 2 O 3 particles with sizes ∼5 nm were formed on the surface of the zeolite matrix. The nano-composite, γ-Fe 2 O 3 @NaY has been subsequently subjected for thorough characterization with several spectroscopic techniques as well as magnetic and transmission electron microscopic measurements. This confirms the formation of maghemite nanoparticles on a NaY-zeolite surface. γ-Fe 2 O 3 @NaY…

Spin crossover of ferric complexes with catecholate derivatives. Single-crystal X-ray structure, magnetic and Mössbauer investigations.

Complexes of general formula [(TPA)Fe(R-Cat)]X·nS were synthesised with different catecholate derivatives and anions (TPA = tris(2-pyridylmethyl)amine, R-Cat2− = 4,5-(NO2)2-Cat2− denoted DNC2−; 3,4,5,6-Cl4-Cat2− denoted TCC2−; 3-OMe-Cat2−; 4-Me-Cat2− and X = BPh4−; NO3−; PF6−; ClO4−; S = solvent molecule). Their magnetic behaviours in the solid state show a general feature along the series, viz., the occurrence of a thermally-induced spin crossover process. The transition curves are continuous with transition temperatures ranging from ca. 84 to 257 K. The crystal structures of [(TPA)Fe(DNC)]X (X = PF6−; BPh4−) and [(TPA)Fe(TCC)]X·nS (X = PF6−; NO3− and n = 1, S = H2O; ClO4− and n = 1, S = H…

Structure and magnetic properties of AgFeP2O7

Abstract AgFeP2O7 has been synthesized by flux crystallization and characterized by single crystal and powder X-ray diffraction (sp. gr. P21/c, a=7.3298(2), b=7.9702(2), c=9.5653(2) A, β=111.842(1)°, V=518.68(2) A3) and FTIR-spectroscopy. The structure is composed of isolated iron octahedra and phosphate tetrahedra interconnected into 3D network with hexagonal channels, where silver counter-ions are located. The magnetic behavior of the compound approaches the Curie–Weiss equation with a Weiss constant θ=−165.9 K indicating strong antiferromagnetic interaction between iron(III) ions.

Spin transition in iron complexes induced by heat, pressure, light and nuclear decay

The phenomenon of temperature-dependent spin transition will be introduced and the numerous chemical and physical influences affecting the spin transition characteristics will be discussed. We shall mainly concentrate on the spin crossover system [Fe(2-pic)3]X2·Sol (2-pic=2-aminomethylpyridine; X=Cl, Br; Sol=C2H5OH, CH3OH) and demonstrate how the behaviour of the spin transition5T2g(Oh)⇌1A1g(Oh) is influenced by substituting the metalion, the non-coordinating anions X, the crystal solvent molecules Sol and by isotopic exchange with H/D and14N/15N. It will also be shown that the spin transition is very susceptible to pressure. A quantitative spin state conversion from low spin to high spin c…

Surface versus bulk composition of a phosphate glass

Transmission and conversion electron Mossbauer spectroscopy as well as photoelectron spectroscopy were applied to study alterations of the surface layer of an iron containing industrial phosphate glass as compared with its bulk. In the surface layer, after polishing and exposure to ambient atmosphere, Fe 2+ is partially oxidized to Fe 3+ . This oxidation, however, does not increase the O/P ratio in this layer, because it goes along with a strong leaching of network modifiers. This leaching leads to a net decrease of the O/P ratio because it overcompensates the relative oxygen increase by Fe 2+ oxidation and by uptake of water

Study of thermal spin crossover in [Fe(II)(isoxazole)(6)](BF4)(2) with Mossbauer spectroscopy

Fe-57 Mossbauer spectroscopy of the mononuclear [Fe( II)( isoxazole)(6)]( BF4)(2) compound has been studied to reveal the thermal spin crossover of Fe( II) between low- spin ( S = 0) and high- spin ( S = 2) states. A temperature-dependent spin transition curve has been constructed with the least- square fitted data obtained from the Mossbauer spectra measured at various temperatures in the 240 - 60 K range during the cooling and heating cycle. The compound exhibits a temperature- dependent two- step spin transition phenomenon with T-SCO ( step 1) = 92 and TSCO ( step 2) = 191 K. The compound has three highspin Fe( II) sites at the highest temperature of study; among them, two have slightly …

A CEMS-study of the passive layer on iron and steel

From AES, ICEMS, and DCEMS experiments it was concluded that the passive layer formed on steel in a phosphate buffer consists of γ-FeOOH. Its thickness increases from 0.5 to 3.5 nm throughout the passive region. It is covered by noncorrelated layers of a precipitate and an adsorbate.

Mössbauer investigation of the photoexcited spin states and crystal structure analysis of the spin-crossover dinuclear complex [{Fe(bt)(NCS)(2)}(2)bpym] (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine).

The crystal structure of the complex [{Fe(bt)(NCS)(2)}(2)bpym] (1) (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine) has been solved at 293, 240, 175 and 30 K. At all four temperatures the crystal remains in the P space group with a=8.7601(17), b=9.450(2), c=12.089(3) A, alpha=72.77(2), beta=79.150(19), gamma=66.392(18) degrees , V=873.1(4) Angstrom(3) (data for 293 K structure). The structure consists of centrosymmetric dinuclear units in which each iron(II) atom is coordinated by two NCS(-) ions in the cis position and two nitrogen atoms of the bridging bpym ligand, with the remaining positions occupied by the peripheral bt ligand. The iron atom is in a severely distorted octahedral FeN(6) e…

Spin Crossover in Fe(II) Molecular Compounds — Mössbauer and µSR Investigations

The compound [Fe(ptz)6](C104)2 (ptz = 1-propyl-tetrazole) displays a complete and gradual spin crossover centred around 125 K as evidenced by magnetic and muon measurements over the temperature range ∼ 4.2–300 K. Although the crystal structure reveals only one crystallographic site, line broadening is observed in the Mossbauer spectra in the vicinity of the spin transition. The muon spin relaxation behaviour of this compound indicates that a structural transformation rather than dynamic processes may account for the observed spectral features. Both the Mossbauer and muon measurements are consistent with a mixture of high and low spin Fe ions in the transition region.

Large negative magnetoresistance effects in Co2Cr0.6Fe0.4Al

Abstract Materials, which display large changes in resistivity in response to an applied magnetic field (magnetoresistance) are currently of great interest due to their potential for applications in magnetic sensors, magnetic random access memories, and spintronics. Guided by striking features in the electronic structure of several magnetic compounds, we prepared the Heusler compound Co2Cr0.6Fe0.4Al. Based on our band structure calculations, we have chosen this composition in order to obtain a half-metallic ferromagnet with a van Hove singularity in the vicinity of the Fermi energy in the majority spin channel and a gap in the minority spin channel. We find a magnetoresistive effect of 30% …

Technical Note:Study of the Cl−-Induced Breakdown of the Passive Layer on Steel

Abstract The Cl−-induced breakdown of the passive layer on a standard steel has an induction time that increases in a nearly linear fashion with the previous holding time (at the passivation potent...

The influence of phosphoric acid on steel and on its corrosion products: a Mössbauer spectroscopic approach

Mossbauer spectroscopy was used to study corroded iron after treatment with phosphoric acid or commercial rust transformers. It was found that treatment produced normal iron phosphates from metallic iron, hematite and FeO, and acid ferric phosphate FeH 3 (POI4I)I2I. 2.5H 2 O from alphaand gamma Fe 2 O 3 and alpha, beta, and gammaFeOOH. When these last are present, phosph oric acid treatment does not produce a protective, inhibiting layer. See also AATA 19-702. -- AATA

Mössbauer Spectroscopic Evidence of Angle-Dependent Intersystem Crossing in LiNbO3:Fe3+

M\"ossbauer emission spectra of LiNb${\mathrm{O}}_{3}$:$^{57}\mathrm{Co}$ single crystals in magnetic fields up to 5 T at 4.2 K show initial populations of the $^{6}A_{1\mathrm{g}}$ Zeeman substates of ${\mathrm{Fe}}^{3+}$ which depend strongly on the angle between the crystallographic $c$ axis and the magnetic field. This is interpreted in terms of a crystal-field effect on excited states which influences the initial populations of the Zeeman sublevels of the $^{6}A_{1\mathrm{g}}$ ground term after the electron-capture decay of $^{57}\mathrm{Co}$. An intersystem crossing process due to orbit-lattice interaction can fairly well explain the angular dependence.

Light-induced excited spin-state trapping of the Fe(ppi)2(NCS)2 complex

MÖSSBAUER EFFECT STUDY ON THE HIGH-SPIN (5T2) ⇌ LOW SPIN (1A1) TRANSITION IN [Fe(2-pic)3]Cl2. DILUTION EFFECT IN [FexZn1-x(2-pic)3] Cl2. EtOH AND CRYSTAL SOLVENT EFFECT

Synthesis, X-ray crystal structure and magnetic study of a μ 1,5-dca bridged ferromagnetic dimeric copper(II) complex

Reaction of Cu(NO3)2 · 3H2O, 1-(N-salicyalideneimine)-2-(N,N-dimethyl)-aminoethane (HL1), LiClO4, and sodium dicyanamide (Nadca) in aqueous medium affords a dimeric complex [Cu2(L1)2 (μ1, 5-dca)](ClO4) (1). Single crystal X-ray analysis reveals that 1 is dinuclear with copper(II) ions bridged by a single dicyanamide group in end-to-end fashion. The coordination environment around copper(II) is square planar. Two nitrogens and oxygen of the tridentate Schiff-base ligand (HL1) occupy three coordination sites of the square plane while the remaining site is occupied by the nitrogen of a terminal nitrile of the bridging dca. The nitrogen of the other terminal nitrile group of the μ1,5-dca ligand…

A study of electrochemically-induced corrosion of low carbon steel in a medium modelling acid rain

Complementary electrochemical, spectrophotometric and electron microsopic investigations were made in addition to the conversion electron Mossbauer spectroscopic (CEMS) measurements to learn more about the mechanism of corrosion of low carbon steel samples in aqueous sulfate and sulfite containing sulfate solutions (pH 3.5, 6.5 and 8.5). Passivation of iron in pure sulfate solution was studied in detail in earlier papers. In the present work, we used a solution containing both sulfate and sulfite anions to obtain more information about the effect of acid rain on low carbon steel samples. The compositions and thicknesses of the passive films formed due to the electrochemical treatments were …

Alternating Chain Magnetism in Catena-μ-Oxo-Hemiporphyrazinatoiron(IV), The First μ-Oxo Linear Chain Complex Of Iron

Abstract X-ray studies, Mossbauer, and magnetism show FeOHp to be an antiferromagneticaly coupled alternating chain with J = -133 cm−1, g = 2.3 and an alternation parameter of 0.4.

Ti2Sn3:  A Novel Binary Intermetallic Phase, Prepared by Chemical Transport at Intermediate Temperature

Ti2Sn3 was obtained by chemical transport using iodine as the transport agent in a sealed quartz ampule at 500 °C. Its crystal structurea new type structurewas determined via single-crystal structure analysis to be orthorhombic, space group Cmca, a = 595.56(4), b = 1996.4(2), c = 702.81(5) pm, V = 835.6(1) × 106 pm3, and Z = 8. The structure can be derived from a three-dimensional condensation of a single polyhedron, which comprises a Ti atom in the center, surrounded by seven Sn and four Ti atoms forming a tri-capped square antiprism. Supporting the results of the self-consistent band structure calculations, Ti2Sn3 is a metallic p-type conductor, exhibiting Pauli paramagnetism and a specif…

The deformation tensor ∊ of the spin transition in the mixed crystal [Fe0.46Zn0.54(ptz)6](BF4)2

The conversion of the spin state of complexes exhibiting thermal spin crossover from the1A1low-spin (LS) state to the5T2high-spin (HS) state is accompanied by a deformation of the lattice due to the larger bond lengths in the HS state as compared with the LS state. In a previous work [Kuszet al.(2000).J. Appl. Cryst.33, 201–205], it has been shown that the deformation of the lattice, corrected for its temperature dependence, can be described by an almost temperature-independent tensor ∊ multiplied by the fraction of molecules in the HS state, γHS. Here the dependence of ∊ in a mixed single crystal of [Fe0.46Zn0.54(ptz)6](BF4)2(ptz = propyltetrazole) with a transition temperature near 110 K …

Bis-macrocyclic Ligands with Two Ferrocenyl End Groups, and Their Tetranuclear Dicopper(I) Compounds

A series of bismacrocyclic ligands with two ferrocenyl groups, exo/endo-1,1‘:1‘ ‘,1‘ ‘‘-[1,2,4,5-tetrakis(5-aza-2-thiahexa-5-enyl)benzene]bisferrocene (exo/endo-FeBeFe), 1,1‘:1‘ ‘,1‘ ‘‘-[1,2:1‘,2‘-tetrakis(5-aza-2-thiahexa-5-enyl)ethene]bisferrocene (1,2-FeEnFe), 1,1‘:1‘ ‘,1‘ ‘‘-[1,1‘:2,2‘-tetrakis(5-aza-2-thiahexa-5-enyl)ethene]bisferrocene (1,1-FeEnFe), 1,1‘:1‘ ‘,1‘ ‘‘-[tetrakis(5-aza-2-thiahexa-5-enyl)methane]bisferrocene (FeMeFe), and their dicopper(I) compounds have been synthesized and characterized (electrochemistry, IR, NMR and Mossbauer spectroscopy). The molecular structure of endo-FeBeFe has been determined by X-ray structure analysis and the copper(I)-induced discrimination of t…

Anodic layers formed on steel in phosphate buffer solution

In-situ gamma scattering and ex-situ conversion electron Mossbauer, and Auger spectroscopy were applied to investigate anodic layers on steel. Samples treated in the active potential range in phosphate buffer solution show a Fe(II)-phosphate deposit on the surface. After treatment in the passive potential region, only Fe3+was found to exist in the oxide layer. The passive layer does not consist of stoichiometric oxidic phases.

New reaction of 1H-pyrazoles with selenium dioxide: one-pot synthesis of bis(1H-pyrazol-4-yl)selenides

Abstract A novel reaction between 3- and 3,5-substituted pyrazoles with selenium dioxide proceeds with formation of bis(3R,5R′-1H-pyrazol-4-yl)selenides in high yield. On this basis, an efficient one-pot synthetic procedure has been developed. In the case of the unsubstituted pyrazole a selenonium compound has been obtained. The identity and structure of the isolated selenium derivatives have been confirmed by spectral methods and their molecular structures investigated by X-ray analysis.

Synthesis, X-ray crystal structure and magnetic study of a dicyanamido bridged 1D chain nickel(II) complex

Abstract Reaction of Ni(NO3)2 · 6H2O and sodium dicyanamide (Nadca) yields a 1D infinite chain complex {[Ni(dien)(μ1,5-dca)(H2O)](NO3)}n (1) (where dien = diethylenetriamine). The coordination environment in complex 1 around the nickel(II) ions is distorted octahedron. Three nitrogen atoms of the ligand diethylenetriamine and an oxygen atom of H2O molecule constitute the four coordination sites of the basal plane of the octahedron. Of two axial positions of the octahedron, one position is occupied by the nitrogen atom of a μ1,5-dca anion the remaining coordination site is occupied by a nitrogen atom of another end-to-end bridging dca from an adjacent [Ni(dien)(μ1,5-dca)(H2O)] moiety, yieldi…

Electronic Spin Crossover

Decacyclene as complexation manifold: synthesis, structure and properties of its Fe2 and Fe4 slipped triple-decker complexes.

Reaction of [(eta(5)-Me4EtC5)Fe(II)Cl(tmeda)] (tmeda = N,N,N'N'-tetramethylethylenediamine) with a polyanion solution of decacyclene (1) results in the formation of the triple-deckers [{(eta(5)-Me4EtC5)Fe}2-mu2-(eta(6):eta(6)-decacyclene)] (3) and [{(eta(5)-Me4EtC5)Fe}4-mu4-(eta(6):eta(6):eta(6):eta(6)-decacyclene)] (4). Metal complexation in 3 and 4 occurs on opposite faces of the pi perimeter in an alternating mode. The decacyclene ring adopts a gently twisted molecular propeller geometry with twofold crystallographic symmetry (C2). Complex 4 crystallizes in the chiral space group C222(1); the investigated crystal only contains decacyclene rings with M chirality. The handedness can be ass…

Mössbauer Spectroscopy

Mössbauer and magnetic studies of mixed-valence linear chain compounds: Na3Fe2S4 and Na3Fe2Se4

Mossbauer and magnetic data establish the two compounds Na3Fe2X4(X=S, Se) as mixed-valence linear chain compounds with rapid valence fluctuation. The compounds exhibit 1-dimensional antiferromagnetic coupling within the chains, and below a critical temperature a 3-dimensional ferrimagnetic ordering between the chains.

CHARACTERIZATION OF IRON COMPOUNDS FROM URBAN AND RURAL AEROSOL SOURCES

Abstract Iron plays an important role in the chemistry and physics (by varying the hygroscopicity) of the atmosphere. Bulk samples were taken from an air-conditioning device, from the electrofilter of a gas–oil power station of the Technical University of and from rural sites near Darmstadt, situated between medium-altitude mountains and with a climate dominated by air masses from the west. Samples were collected in urban and rural (meadow) air, from different waste incineration power stations, from the exhausts of a gasoline and from a diesel motor car, and from a private gas fired heating system. The samples were characterized for elemental composition by total reflection X-ray fluorescen…

Mössbauer mineralogy of rock, soil, and dust at Meridiani Planum, Mars: Opportunity's journey across sulfate-rich outcrop, basaltic sand and dust, and hematite lag deposits

Additonal co-authors: P Gutlich, E Kankeleit, T McCoy, DW Mittlefehldt, F Renz, ME Schmidt, B Zubkov, SW Squyres, RE Arvidson

Discrete bond model (DBM) of sodium silicate glasses derived from XPS, Raman and NMR measurements

In sodium silicate glasses, the fraction of differently bound Si species Q[i] (i = 0−4), depending on the number i of bridging oxygens bound to the quarternary silicon, is a function of stoichiometry and the Na/Si ratio. Sodium silicate glasses were investigated by high resolution X-ray photoelectron spectroscopy. To explain the differences in chemical shifts and linewidths of the O 1s signal of the bridging and the non-bridging oxygen as a function of alkali concentration, and extended glass model was developed. This new model takes into account the influence of the alkali concentration on the Q[i] distribution and on the appearance and concentrations of differently bound bridging oxygens …

Mössbauer-Active Transition Metals Other than Iron

The previous chapters are exclusively devoted to the measurements and interpretation of 57Fe spectra of various iron-containing systems. Iron is, by far, the most extensively explored element in the field of chemistry compared with all other Mossbauer-active elements because the Mossbauer effect of 57Fe is very easy to observe and the spectra are, in general, well resolved and they reflect important information about bonding and structural properties. Besides iron, there are a good number of other transition metals suitable for Mossbauer spectroscopy which is, however, less extensively studied because of technical and/or spectral resolution problems. In recent years, many of these difficult…

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

Mossbauer spectroscopy was founded more than fifty years ago based on an outstanding discovery by the young German physicist Rudolf Ludwig Mossbauer 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 s…

Spin Transition Molecular Materials: New Sensors

This short review article concerns a new family of iron(II) spin transition chain compounds containing 4-R-1,2,4-triazole derivatives whose properties have been followed by several physical techniques. A clear evidence of the LIESST effect at 20 K has been found for one of these materials by 57Fe Mossbauer spectroscopy. Potential applications in terms of pressure and thermal sensors are discussed.

The role of nano-sized iron particles in slurry phase Fischer–Tropsch synthesis

Abstract The slurry phase Fischer–Tropsch (F–T) activity of three α-Fe2O3-based materials, two unsupported nano-sized, NANOCAT (3 nm) and BASF (20–80 nm), and a supported micron-sized (32.5 μm ) UCI, are compared with respect to total hydrocarbon production from synthesis gas (H2/CO∼2/1) at 513 K. Low temperature Mossbauer spectra of the quenched slurry samples after 120 h on-line show that all three catalysts are essentially a mixture of oxide and carbide phases with magnetite (Fe3O4) being the dominant phase. TEM images of the quenched samples reveal unexpected particle characteristics. While both unsupported nano-sized materials essentially avoid expected agglomeration, the micron-sized …

Magnetic properties and61Ni Mössbauer spectroscopy of the ternary phosphide CrNiP

The results of x-ray diffraction, dc magnetization, and 61Ni Mossbauer spectroscopy studies of the ternary phosphide CrNiP are reported. This compound crystallizes in the orthorhombic Co2P-type structure (space group Pnma) with the lattice parameters a = 5.7965(1) A, b = 3.5337(1) A, and c = 6.8123(2) A. NiCrP is a ferromagnet with Curie temperature TC = 135.1(1) K. The ferromagnetic-to-paramagnetic transition is characterized by the critical exponents β = 0.355(22), γ = 1.241(18), and δ = 4.585(20). Their values are close to those of a 3D Heisenberg ferromagnet. The temperature dependence of the magnetic susceptibility above TC follows the modified Curie–Weiss law with a paramagnetic Curie…

Formation and characterization of oxidic and metallic Fe/Ni multilayers prepared from Langmuir-Blodgett films

Oxidic and metallic iron, nickel, and mixed iron/nickel mono- and multilayers were prepared by some treatments of iron- and nickel-containing Langmuir-Blodgett films. The layers were characterized by several surface-sensitive methods. Interactions between the iron and the nickel could be observed. The results are different to those obtained from disordered bulk alloys and from simple diffusion calculations.

Soft-Chemical Growth ofγ-FeO(OH) Films on Self-Assembled Monolayers of Substituted Alkylthiols on Gold(111)

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

The stoichiometric iron nitrides γ′-Fe4N, e-Fe3N and ζ-Fe2N were characterized by Mossbauer spectroscopy. The thermal decomposition of e-Fe3N was studied in-situ by means of a specially developed Mossbauer furnace. We found e-Fe3N to γ′-Fe4N and e-Fe3Nx (x ≥ 1.3) as decomposition products and determined the border of γ′/e transformation at T ≅ 930 K. Mossbauer spectroscopy was applied to study in-situ the thermal decomposition of the nitridometalate Li3[FeIIIN2] and the formation of Li2[(Li1-xFeIx)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[(Li1-xFeIx)N] was of particular interest in …

Multifunctionality in spin crossover materials

Abstract One of the most important trends in the spin crossover (SCO) field is focused on the synthesis of new molecule-based functional materials in which the SCO properties may be combined with other physical or chemical properties in a synergic fashion. The current stage of investigations regarding interplay and synergic effects between SCO, magnetic coupling, liquid crystalline properties, host–guest interactions, non-linear optical properties, electrical conductivity, and ligand isomerization is highlighted and discussed.

Anomalous pressure dependence of the Lamb-Mössbauerf-factor in the spin crossover system [Fe(2-pic-ND2)3]Cl2·EtOD

The pressure dependence of the Lamb-Mossbauer factor of the spin crossover compound [Fe(2-pic-ND2)3]Cl2·EtOD(2-pic-ND2=2-picolylamine, deuterated at the−NH2 group) has been measured at pressures up to 1500 bar and at three temperatures (115.7, 146.7, 185.6 K) around the transition temperatureT t=135 K. The temperature dependence of the unit cell volume has been determined by X-ray diffraction. In the transition region (T=146.7 K), the pressure dependence of thef-factor shows an anomalous increase as compared to the dependence below and above the transition. The behaviour off(p, T), its anomaly and absolute value, can be consistently explained within a theoretical model which treats the comp…

CCDC 975036: Experimental Crystal Structure Determination

Related Article: Maksym Seredyuk, M. Carmen Muñoz, Vadim Ksenofontov, Philipp Gütlich, Yury Galyametdinov, and Jose A. Real|2014|Inorg.Chem.|53|8442|doi:10.1021/ic5010159

CCDC 975041: Experimental Crystal Structure Determination

Related Article: Maksym Seredyuk, M. Carmen Muñoz, Vadim Ksenofontov, Philipp Gütlich, Yury Galyametdinov, and Jose A. Real|2014|Inorg.Chem.|53|8442|doi:10.1021/ic5010159

CCDC 975039: Experimental Crystal Structure Determination

Related Article: Maksym Seredyuk, M. Carmen Muñoz, Vadim Ksenofontov, Philipp Gütlich, Yury Galyametdinov, and Jose A. Real|2014|Inorg.Chem.|53|8442|doi:10.1021/ic5010159

CCDC 975037: Experimental Crystal Structure Determination

Related Article: Maksym Seredyuk, M. Carmen Muñoz, Vadim Ksenofontov, Philipp Gütlich, Yury Galyametdinov, and Jose A. Real|2014|Inorg.Chem.|53|8442|doi:10.1021/ic5010159

CCDC 975038: Experimental Crystal Structure Determination

Related Article: Maksym Seredyuk, M. Carmen Muñoz, Vadim Ksenofontov, Philipp Gütlich, Yury Galyametdinov, and Jose A. Real|2014|Inorg.Chem.|53|8442|doi:10.1021/ic5010159

CCDC 975040: Experimental Crystal Structure Determination

Related Article: Maksym Seredyuk, M. Carmen Muñoz, Vadim Ksenofontov, Philipp Gütlich, Yury Galyametdinov, and Jose A. Real|2014|Inorg.Chem.|53|8442|doi:10.1021/ic5010159