Low temperature Mössbauer spectra and magnetic ordering of lithiated ferric molybdate: Li2Fe2(MoO4)3

Powder x-ray diffraction, variable temperature magnetic susceptibility, and zero field Mössbauer spectroscopy measurements were used to characterize the new phase Li₂Fe₂ (MoO₄)₃. This material is obtained topochemically simply by the mixing of solutions of lithium iodide in acetonitrile with solid Fe₂(MoO₄)₃ at ambient temperature. Li₂Fe₂(MoO₄)₃ possesses the high temperature orthorhombic ferric molybdate $$\begin{gathered} Fe_2 (MoO_4 )_3 + 2LiI\xrightarrow{{CH_3 CN}}Li_2 Fe_2 (MoO_4 )_3 + I_2 \hfill \\ (solid)(solution)(solid)(solution) \hfill \\ \end{gathered}$$ structure. Guinier photographs were completely indexed in space group Pnca. Magnetic hyperfine splitting of the zero field Mössbauer spectrum below 12.5 K indicates a three-dimensional magnetically ordered state which susceptibility results show to be weakly ferromagnetic owing to probable canting of antiferromagnetically coupled sublattices.     

On the low temperature magnetic properties of some sulfites of divalent iron

Zero field Mössbauer spectra and powder susceptibility measurements show that the condensed, hydrogen bonded network compound FeSO₃ 3H₂O orders antiferromagnetically (T_Néel 9.5 K). The related anhydrous material FeSO₃ also shows antiferromagnetic exchange but no evidence of long range three-dimenstional magnetic order to as low as 1.4 K.Supported by the U.S. National Science Foundation Division of Materials Research—Solid State Chemistry Program Grant No. DMR 8313710.     

Mössbauer spectroscopy evidence for reductive loss of bromine from C60Br24 in reactions of halogenated C60 with ferrocene

Reactions of ferrocene (C₅H₅)₂Fe with halogenated fullerenes C₆₀X _n for X=F, Cl, Br andn = 15–39) yield non-stoichiometric solids with intense singlet Mössbauer spectra characteristic of Cp₂Fe₊ (where Cp=C₅H₅). The material isolated from reaction of Cp₂Fe with C₆₀Br₂₄ exhibits two different iron environments and magnetic ordering temperatures of 14 K and between 4.6 and 1.32 K. These data are seen to be consistent with loss of bromine from the fullerene and formation of ferricenium tetrahaloferrate salts.     

Anion dependence of the valence state detrapping behavior for a fused hydrocarbon bridged binuclear mixed valence iron compound and its di-oxygen sensitivity

Monocationic forms of the symmetric and asymmetric indacene bridged species [(Cp^*Fe)₂(-s-indacene)],I, and [(Cp^*Fe)₂(-as-indacene)],II, are fully detrapped and trapped, respectively, over the entire range from 1.5 K to ambient temperature as their BF ₄ ^– salts. In contrast to [II ⁺][BF ₄ ^– ], the TCNE^.– salt [II ⁺][TCNE^.–] exhibits a transition from fully trapped to a largely detrapped valence state behaviour over the increasing temperature range 100 to 300 K. Mössbauer spectra ofI suggest that while it is relatively insensitive to oxygen as a neat solid, it is strongly oxidized by O₂ in dry hexane solution. Similar studies ofII indicate essential insensitivity to O₂, both as a solid and in hexane solution.     

Low temperature magnetic ordering of a series of structurally characterized chloroferrates

Iron-57 Mössbauer spectroscopic results for a new series of related chloroferrate salts of complex ammonium cations are presented. In particular, spectra of materials based on FeCl ₄ ^– , FeCl ₅ ^2– , FeCl ₆ ^– , [FeCl₅(H₂O)]^2–, and [FeCl₅(CH₃OH)]^2– anions are discussed relative to the systematics of their isomer shifts, coordination numbers, and low temperature 3D critical ordering temperatures. The following specific systems have been studied by Mössbauer spectroscopy and definitively characterized by single-crystal X-ray analysis: [CH₃NH ₃ ⁺ ]₄[FeCl₆]^3–[Cl^–](A), [Me₂N(-CH₂CH₂)₂NMe ₂ ⁺ ][FeCl ₅ ^2– ] (B), [H₃NCH₂CH₂NH ₃ ²⁺ ][FeCl₅·H₂O^2–], (C), and [NH₃(CH₂)₆NH ₃ ²⁺ ]₄[(FeCl ₆ ^3– )(FeCl ₄ ^– )ClCl ₄ ^– ] (D). The spectral data for these complexes are considered in the light of results of previous studies for systems such as [K₂FeCl₅·H₂O], [Co(NH₃)₆][FeCl₆], diamethyltriethylenediammoniumpentachloroferrate (E), and the related [FeCl₅·CH₃OH]^2– salt (F). The critical 3D ordering temperatures are 1.45, 6.80, 3.45, and 1.22K forA, B, C, andD, respectively.     

Poly[(2,2'-bipyridine)tetrakis(imidazolato)diiron(II)]: structural and spin-state phase transitions and low-temperature magnetic ordering in a unique 2-dimensional material

Poly[(2,2'-bipyridine)tetrakis(imidazolato)diiron(II)] was synthesized by the reaction of ferrocene with imidazole in an excess of 2,2'- bipyridine in a Carius tube at 130 degrees C. Dc magnetic susceptibility studies at an applied field of 1000 G reveal that on cooling from room temperature, the material undergoes two structural phase transitions designated alpha --> beta and beta --> gamma at 151 and 133 K, respectively. On warming, the gamma --> beta and beta --> alpha transitions are observed at 137 and 151 K, respectively; a 4 K thermal hysteresis clearly detectable in the lower temperature beta <--> gamma transition. These structural phase transitions have also been studied by detailed, variable-temperature, ac susceptibility and M?ssbauer spectroscopy techniques. Single-crystal X-ray diffraction studies done at 294, 143, and 113 K reveal 2, 12, and 6 unique iron centers in the alpha-, beta-, and gamma-forms, respectively. All three forms have the same basic structure involving 2D extended double layer sheets (bilayers) of alternating tetrahedral and octahedral irons singly bridged by imidazolate ligands, with the octahedral centers additionally coordinated by 2,2'-bipyridine ligands that occupy positions between the sheets. Magnetic susceptibility and bond length data reveal that in the gamma-phase one in three six-coordinate sites corresponds to spin singlet ground-state iron(II); i.e., the overall alpha --> gamma process involves a spin-crossover transition such that at least 1/6 of the iron sites in the gamma-phase correspond to S = 0. This is supported by the low-temperature M?ssbauer spectra of the gamma-phase, which reveal the simultaneous presence of both S = 2 and S = 0 iron(II) centers. The compound magnetically orders, with a resultant small remnant magnetization, at low temperatures. The magnetic phase transition, studied by a combination of dc and ac susceptibility and M?ssbauer techniques, occurs at T(c) approximately 6.5 K.     

Magnetic superexchange involving the oxygen-sulfur-oxygen pathway of the sulfate ion: A Mössbauer spectroscopy and magnetic susceptibility study of Fe(2,9-di-CH3-phenanthroline) SO4

Zero-field Mössbauer spectra of powder samples of Fe(2,9-di-CH₃-phenanthroline) SO₄ over the range 1.7 to 300°K show a large (～ 3.6 mm/sec) temperature-independent quadrupole splitting corresponding to an orbital singlet ground term. The chemical isomer shift, δ_FE=O, is 1.16 mm/sec (source and absorber at 4.2°K) corresponding to six coordinate high-spin iron (II). Below 4.2°K, the compound exhibits magnetic hyperfine splitting suggesting slow relaxation and the possibility of long-range three-dimensional magnetic ordering with a critical temperature T_c such that 3.5°K < T_c < 4.2°K and an internal hyperfine field H_n = 325 kG at 1.69°K. High-field Mössbauer spectra at 300°K indicate that the principal component of the electric field gradient tensor is positive and axial. Similar spectra at 4.2°K show an absence of nuclear Zeeman splitting for applied fields up to 60 kG, and indicate that at 4.2°K the material is rapidly relaxing but with substantial magnetic polarization and a negative internal hyperfine field. The temperature dependence of the magnetic susceptibility confirms antiferromagnetic interactions with a broad maximum χ′_M at ～ 11.8°K presumably due to low-dimensionality exchange interactions (possibly one) along MOSOM chains. Least-squares fits of χ′_M^?1 versus T for T50°K indicate (Curie-Weiss behavior with C = 3.26 emu/mole, θ = -21.95°K, and μ_eff = 5.11.     

Observation of a very large internal hyperfine field (62.4 T) in the ferromagnetically ordered state of the S = 1 alpha-iron(II) octaethyltetraazaporphyrin

The origins of the extraordinarily large internal hyperfine field (62.4 T) for the three-dimensional (weak) ferromagnetically ordered ground state of alpha-Fe(OETAP) are discussed semiquantitatively in terms of existing physical theory. In particular, the classical Fermi-contact contribution to the internal field is found to be highly enhanced by a very large orbital contribution and a significant dipolar term of the same sign. A rationale for the unexpected ordering of this S = 1 non-Kramers system is also presented.     

On the potentialities of nuclear gamma resonance (Mössbauer effect) spectroscopy as a new,low dose approach to cancer radiation therapy

The extension of a new, low dose, Mössbauer spectroscopy approach to cancer radiation therapy to “easy” isotopes other than Iron-57 is outlined. New in vitro studies using a number of cancer cell lines are reported.