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…

Preparative and spectroscopic features of ferricenium tetrachloroferrate(III). Interconversion to diferricenium ?-oxo-bis[trichloroferrate(III)]

Ferricenium tetrachloroferrate(III)(1), one of the more frequently cited ferricenium salts, has recently attracted biomedical interest because of its pronounced antineoplastic activity against Ehrlich ascites murine tumor. In this paper, synthetic methods are reinvestigated in an effort to prepare pure(1) free from a common contaminant, diferriceniumμ-oxo-bis(trichloroferrate)(3). The oxodiferrate, or mixtures of this salt with(1), can readily be converted into pure(1) under acidic conditions. Conversely, dimerization of(1) with participation of water to give the oxodiferrate(3) is brought about by recrystallization of the former from moist acetonitrile/methanol in the presence of base; thi…

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

Chemical characterization of iron in atmospheric aerosols

Abstract The total Fe content, the soluble fractions of Fe(II) and Fe(III), and several species of Fe were determined in various atmospheric aerosol samples by means of atomic absorption spectrometry, ion chromatography and Mossbauer spectrometry.

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…

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…

ChemInform Abstract: Ferric Phosphite: Dimers of Face-Sharing Fe(III)O6 Octahedra. Crystal Structure Redetermination, Moessbauer Spectra, Magnetic Susceptibility, and Heat Capacity Data.

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

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.

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. >

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…

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 …

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

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.

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…

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.

Spin crossover in hexakis(1-(2-chloroethyl)-tetrazole)iron(II) complexes; synthesis and magnetic properties

Abstract The spin-crossover complexes [Fe(teec)6](X)2 (with teec=1-(2-chloroethyl)-tetrazole and X=BF4, ClO4, PF6) possess two iron(II) sites each having a different spin-crossover behaviour. The magnetic behaviour of the complexes obtained by slow crystallisation differs strongly from those obtained by precipitation. This difference results in either a spin crossover of 50% (X=ClO4, crystalline), two gradual steps (X=BF4, PF6), or two steps, of which one is gradual and the other having a thermal hysteresis (X=ClO4 precipitated). Both 57Fe Mossbauer spectroscopy and magnetic susceptibility measurements have been recorded as a function of T. The crystal structure of [Fe(teec)6](BF4)2 has bee…

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 …

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…

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…

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…

Structural and magnetic properties of the solid solution series Sr2Fe1–xMxReO6(M = Cr, Zn)

Strong correlations between the electronic, structural and magnetic properties have been found during the study of doped double perovskites Sr2Fe1−xMxReO6 (0 ≤ x ≤ 1, M = Zn, Cr). The interplay between the van Hove singularity and the Fermi level plays a crucial role for the magnetic properties. Cr doping of the parent compound Sr2FeReO6 leads to a non-monotonic behaviour of the saturation magnetization and an enhancement for doping levels up to 10%. The Curie temperatures monotonically increase from 401 to 616 K. In contrast, Zn doping leads to a continuous decrease in the saturation magnetization and the Curie temperatures. Superimposed on the electronic effects is the structural influenc…

Iron-Promoted Nucleophilic Additions to Diimine-Type Ligands:  A Synthetic and Structural Study

We report here three examples of the reactivity of protic nucleophiles with diimine-type ligands in the presence of Fe(II) salts. In the first case, the iron-promoted alcoholysis reaction of one nitrile group of the ligand 2,3-dicyano-5,6-bis(2-pyridyl)-pyrazine (L1) permitted the isolation of an stable E-imido-ester, [Fe(L1')(2)](CF(3)SO(3))(2) (1), which has been characterized by spectroscopic studies (IR, ES-MS, Mössbauer), elemental analysis, and crystallographically. Compound 1 consists of mononuclear octahedrally coordinated Fe(II) complexes where the Fe(II) ion is in its low-spin state. The iron-mediated nucleophilic attack of water to the asymmetric ligand 2,3-bis(2-pyridyl)pyrido[3…

Crystal structure and mössbauer spectroscopy studies of the ferrimagnetic complex bimetallic salt hexaamminechromium (III) hexachloroferrate (III), [Cr(NH3)6][FeCl6]

The crystal and molecular structures of the ferrimagnetic bimetallic complex salt hexaamminechromium(III) hexachloroferrate(III), [Cr(NH3)6][FeCl6], have been determined from single-crystal, three-dimensional x-ray diffraction counter data. The compound crystallizes as orange coloured crystals in the space groupC2/c of the monoclinic system with Z=4 and has cell dimensionsa=11.325(1) A,b=11.387(1) A,c=11.233(1) A, and β=90.83(1)A. The structure was refined by using segmented block diagonal least-squares techniques to discrepancy indices R and Rw of 0.0233 and 0.0285, respectively. The metal ions occupy sites with symmetry $$\bar 1$$ and are nearly octahedrally coordinated. In the [FeCl6]3− …

Polarized neutron diffraction and Mössbauer spectral study of short-range magnetic correlations in the ferrimagnetic layered compounds(PPh4)[FeIIFeIII(ox)3]and(NBu4)[FeIIFeIII(ox)3]

Short-range antiferromagnetic correlations have been studied in the layered compounds (PPh 4 ) [Fe I I Fe I I I (ox) 3 ] and (NBu 4 ) [Fe I I Fe I I I (ox) 3 ] by neutron polarization analysis and Mossbauer spectroscopy. Polarized neutron diffraction profiles obtained between 2 and 50 K on (d 2 0 -PPh 4 ) [Fe I I Fe I I I (ox) 3 ] show no magnetic Bragg scattering; the lack of such scattering indicates the absence of long-range magnetic order. However, a broad asymmetric feature observed at a Q of ca. 0.8 A - 1 is attributed to two-dimensional short-range magnetic correlations, which are described by a Warren function. The correlation length is ca. 50 A between 2 and 30 K and then decreases…

Mössbauer Spectral Study of Two Layered Honeycomb Molecular Magnets: PPh4FeIIFeIII(ox)3 and NBu4FeIIFeIII(ox)3

The Mossbauer spectra of the layer ferrimagnets PPh4FeIIFeIII(ox)3 and NBu4FeIIFeIII(ox)3 have been measured between 1.9 and 315 K. The paramagnetic spectra exhibit both high-spin iron(II) and iron(III) doublets. The iron(II) quadrupole splittings are negative and decrease substantially upon cooling as a result of a low-symmetry crystal field splitting. In contrast, the iron(III) splittings are small, positive, and virtually independent of temperature. The respective magnetic ordering temperatures of 30 and 42.5 K agree well with the phase observed by bulk magnetometry and the magnetic sextets yield hyperfine fields of ca. 60 kOe for iron(II) and 540 kOe for iron(III). The unusually low iro…

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…

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.

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…

Synthesis and characterization of a new family of bi-, tri-, tetra-, and pentanuclear ferric complexes.

Nine members of a new family of polynuclear ferric complexes have been synthesized and characterized. The reaction of Fe(O(2)CMe)(2) with polydentate Schiff base proligands (H(2)L) derived from salicylidene-2-ethanolamine, followed in some cases by reaction with carboxylic acids, has afforded new complexes of general formulas [Fe(2)(pic)(2)(L)(2)] (where pic(-) is the anion of 2-picolinic acid), [Fe(3)(O(2)CMe)(3)(L)(3)], [Fe(4)(OR)(2)(O(2)CMe)(2)(L)(4)], and [Fe(5)O(OH)(O(2)CR)(4)(L)(4)]. The tri-, tetra-, and pentanuclear complexes all possess unusual structures and novel core topologies. Mössbauer spectroscopy confirms the presence of high-spin ferric centers in the tri- and pentanuclear…

Cyano-bridged structures based on [MnIIN3O2-macrocycle)]2+: a synthetic, structural, and magnetic study.

Reactions between the complex [MnII(L)]2+, where L is a N3O2 macrocyclic ligand, and different cyanometalate precursors such as [M(CN)n]m- (M(III) = Cr, Fe; M(II) = Fe, Ni, Pd, Pt) lead to cyano-bridged molecular assemblies exhibiting a variety of structural topologies. The reaction between [MnII(L)]2+ and [FeII(CN)6]4- forms a trinuclear complex with formula [(MnII(L)(H2O))2(FeII(micro-CN)2(CN)4)] x 2MeOH x 10H2O (1) which crystallizes in the triclinic space group P1. The reaction between [MnII(L)]2+ and [M(II)(CN)4]2-, where M(II) = Ni (2), Pd (3), Pt (4), gives rise to three isostructural linear chain compounds with stoichiometry [(MnII(L))(M(II)(micro-CN)2(CN)2)]n and which crystallize …

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.

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…

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% …

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

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…

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 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…

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