EPR Features of Spin-Crossover in Tris(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dialkyl-Dithiocarbamato)Iron(III)

The temperature dependence of electron paramagnetic resonance (EPR) spectra of a series of dithiocarbamates Fe(RR′dtc)₃ was studied in the temperature range from 5 to 300 K. A small part of solvated complexes serving as spin probes in the EPR-silent matrix enabled the observation of EPR of the Fe(III) ion in the whole temperature range. The spin transition was revealed in the reduction of the integral intensity of the signal from the high-spin complexes and in the non-monotonous change of the line width with temperature decrease due to the effect of the low-spin complexes with short spin–lattice relaxation times. Below ca. 60 K, the ferromagnetic ordering of the magnetic moments in low-spin particles (“domains”) arising at the spin transition was observed.     

Magnetic Properties and Spin Crossover in Transition Metal Oxides with d 5 Ions at High Pressures

We analyze the influence of cooperative effects on the magnetic properties and spin crossover between the high-spin (HS) term S = 5/2 and low-spin (LS) term S = 1/2 in Mott–Hubbard dielectrics with 3d5 ions under high pressures. Two cooperation mechanisms (superexchange interaction and effective interaction via the elastic system) are considered. The sign of the exchange interaction changes because of the crossover from the antiferromagnetic in the HS state to the ferromagnetic in the LS state. In view of the large difference between the ionic radii of the HS and LS states, the systems with spin crossover acquire an additional strong coupling via the elastic system. Using the Hubbard operator representation and considering the electronic states of the two terms simultaneously, we obtain the effective Hamiltonian with allowance for the cooperative effects. The magnetic phase diagram and the spin crossover are investigated in the mean field approximation. It is shown that the inclusion of cooperative effects at low temperatures leads to a first-order phase transition between the antiferromagnetic HS state and the ferromagnetic LS state. At higher temperatures, more complicated sequences of phase transitions are possible upon an increase in pressure, including the HS paramagnet–HS antiferromagnet–LS paramagnet and HS antiferromagnet–LS paramagnet–LS ferromagnet transitions.     

Fe（II）-NH(a1Δ)N4S2自旋翻转单分子磁体的电子输运性质

Spin-crossover (SCO) magnets can act as one of the most possible building blocks in molecular spintronics due to their magnetic bistability between the high-spin (HS) and low-spin (LS) states. Here, the electronic structures and transport properties through SCO magnet Fe(II)-N₄S₂ complexes sandwiched between gold electrodes are explored by performing extensive density functional theory calculations combined with non-equilibrium Green''s function formalism. The optimized Fe-N and Fe-S distances and predicted magnetic moment of the SCO magnet Fe(II)-N₄S₂ complexes agree well with the experimental results. The reversed spin transition between the HS and LS states can be realized by visible light irradiation according to the estimated SCO energy barriers. Based on the obtained transport results, we observe nearly perfect spin- filtering effect in this SCO magnet Fe(II)-N₄S₂ junction with the HS state, and the corresponding current under small bias voltage is mainly contributed by the spin-down electrons, which is obviously larger than that of the LS case. Clearly, these theoretical findings suggest that SCO magnet Fe(II)-N₄S₂ complexes hold potential applications in molecular spintronics.     

EPR Studies of DOPA–Melanin Complexes with Fe(III)

Paramagnetic centers in 3,4-dihydroxyphenylalanine–melanin and its complexes with Fe(III) were examined by electron paramagnetic resonance (EPR) spectroscopy. Paramagnetic centers of melanin play an important role in detoxification of environment and they reveal high activity in binding of metal ions. Two different signals were observed in EPR spectra: lines of o-semiquinone free radicals and lines of paramagnetic Fe(III). Amplitudes of EPR lines of both free radicals and iron ions decrease with increasing Fe(III) content in melanin–metal ion complexes. Free radical concentrations in the melanin samples, g-factors, amplitudes and line widths of EPR spectra were determined. It was stated that fast spin–lattice relaxation processes exist in both free radical system and paramagnetic iron ions in melanin complexes.     

Pressure,temperature and light influence on spin transition solids

Abstract

Present paper is an overview of our efforts during the past few years to understand complicated corelations of physical phenomena related to pressure in Fe(I1) solid state spin transition systems. Some principal results concerning p, T, λ-experiments are extracted. In the context of correlation of the crystallographic phase transition with simultaneous HS → LS relaxation and LS → HS photopopulation, we show the latest results: Brillouin and magnetic measurements on the crystal [Fe(pt₆](BF₆)₂.     

Fe(II) spin-crossover compounds based on the extremely versatile ligand system of 1-substituted tetrazoles: a comparative study

Bulk measurements of magnetic susceptibility χ and ⁵⁷Fe-Mössbauer spectroscopy were used to investigate the low spin (LS) to high spin (HS) transition caused by temperature changes for different mono- and polynuclear Fe(II) complexes based on the extremely versatile class of 1-substituted tetrazoles. The influence of length and rigidity of different terminating and bridging ligands is shown.     

Hydrostatic pressure driven spin,volume and band gap collapses in SmFeO3: a GGA + U study

The crystal structure, magnetic and electronic properties of SmFeO₃ under hydrostatic pressure have been studied by first-principles calculations within the generalized gradient approximation plus Hubbard U (GGA + U). The iso-structural phase transition with spin, volume and band gap collapses can be induced by a large enough hydrostatic pressure. The high-spin (HS) state of Fe³⁺, with the magnetic moment of ~4 μ_B, is retained at low pressure. The spin crossover occurs at a transition pressure (~68 GPa) with the magnetic moment of Fe³⁺ decreasing to ~1 μ_B in low-spin (LS) state. Meanwhile, the reductions of cell volume (by ~?5.43%) and band gap (from >2 eV to ~1.6 eV) of SmFeO₃ are obtained when the HS–LS transition happens. Finally, the critical pressure of HS–LS transition, magnetic and electronic properties are found to be Hubbard U dependent.     

Specific features of spin-variable properties of [Fe(acen)pic<Subscript>2</Subscript>]BPh<Subscript>4</Subscript> · <Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O

The [Fe(acen)pic₂]BPh₄ · nH₂O compound has been synthesized and studied in the temperature interval of 5–300 K by the methods of EPR and magnetic susceptibility. The existence of ferromagnetic interactions between Fe(III) complexes in this compound has been revealed, in contrast to unhydrated [Fe(acen)pic₂]BPh₄. The reduction in the integrated intensity of the magnetic resonance signal as the temperature decreases below 80 K has been explained by the transition of high-spin ions to the low-spin state. It has been shown that the phase transition temperature in the presence of intermolecular (ferromagnetic) interactions is lower than that in the case of noninteracting centers.     

Influence of the outersphere anion on the properties of the spin transition in Fe(4-OCH3-SalEen)2 Y ( Y = PF6, NO3)

The spin transition from a high-spin state to a low-spin state of Fe(III) ions in the compounds Fe(4-OCH₃-SalEen)₂ Y (Y = PF₆, NO₃) is investigated using the electron paramagnetic resonance (EPR) method. It is established that, unlike the compound with the PF₆ anion, the compound with the NO₃ anion is characterized by a temperature hysteresis of the properties of the spin transition. The thermodynamic characteristics of the spin transitions are determined from the EPR data. It is demonstrated that the specific features of the thermal evolution of the formation of the low-spin complexes are consistent with the domain model of the development of the spin transition. Original Russian Text ? T.A. Ivanova, I.V. Ovchinnikov, A.N. Turanov, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 11, pp. 2033–2038.     

Spin-State Transitions in an Iron Spin-Crossover Complex Observed with X-ray Emission and X-ray Absorption

The thermal- and photon-induced phase transitions of [Fe(2-pic) 3 ]Cl 2 EtOH from a high-spin (HS) state ( S = 2) to a low-spin (LS) state ( S = 0) were observed by X-ray Emission Spectroscopy (XES) and X-ray Absorption Spectroscopy (XAS). The spin state was observed with Fe 3p-1s XES from the HS and photon-induced (PI) phase took S = 2 and LS state took S = 0. Each spectrum of the decay process from the PI phase to the LS state could be described with the superposition of those of the HS and LS states. In XAS, a different spectrum was also observed in the HS and LS states, and likewise by XES; the difference in the pre-edge structure between the HS and LS states was explained based on the difference of Fe unoccupied 3d partial density of state calculated by the DV-X f method.     

Binding of MRI contrast agents to albumin: a high-field EPR study

High-field electron paramagnetic resonance (EPR) experiments to monitor binding of lipophilic Gd(III) complexes to human serum albumin (HSA) are described. It was observed that magnetic interactions between the nitroxide moiety ofn-doxyl-stearic acids bound to HSA and Gd(III) complexes resulted in broadening of nitroxide continuous-wave EPR spectra. The broadening effect can be well described by a one-parameter model of additional Lorentzian broadening At 95 GHz, continuous-wave EPR spectra from Gd(III) complexes are fully resolved from the nitroxide signal allowing for simultaneous and independent line shape analysis. Analysis of the line width broadening effects for spectra from a series ofn-doxyl-stearic acids bound to HSA indicated a progressive decrease of spin label-Gd(III) magnetic interactions along the fatty acid (FA) binding channel, consistent with binding of Gd-DOTAP complex in the vicinity of the main FA binding site. The substantial difference in spin label-metal interactions along the FA binding channel for lipophilic Gd(III) complexes with different chelates is indicative of binding to different sites. We also report measurements of dissociation constant for noncovalent binding of Gd(III) complexes to HSA on the basis of analyses of 95 GHz Gd(III) EPR line shapes.     

An EPR study of the orientational transition in smectic liquid crystals in a magnetic field

Spin probe EPR spectroscopy is used to detect an orientational transition in the smectic mesophase in 4-n-octyl-4'-cyanobiphenyl (8CB) liquid crystal under the action of an intense magnetic field (5.87 T).     

Monte Carlo study of low/high spin transitions

We study the finite temperature property of a model on two dimensional square lattices with two Ising spins at each lattice site by Monte Carlo simulations. When those Ising spins at a lattice site are parallel the site is said to be in the high-spin state (HS), while when they are antiparallel the site is said to be in the low-spin state (LS). Throughout the study, the energy of HS is presumed to be higher than that of LS. Two Ising spins at each site are added to form a total spin, which interacts with its nearest neighbour total spins via spin-spin couplings. The spin-phonon coupling also is introduced via harmonic springs between nearest neighbour sites with spring constants and equilibrium distances depending on the spin states of the sites involved. In this system, we investigate the feature of transitions between LS and HS (to be called low/high spin transition (LHST)) by varying the temperature. As for the ferromagnetic interaction between total spins, the second order phase transition: pure HSmixed state of HS and LS is possible to occur in a pure spin system, as is expected from mean field calculations. The role of lattice distortions by the change of lattice spacings is shown to be essential for LHST: pure LS(pure)HS. In the model investigated, there appears an indication of the strong first order phase transition which reveals a conspicuous hysteresis.     

The spin-crossover complex [Fe(tpa)(NCS) 2 ]

The temperature-induced spin crossover of iron(II) in the [ Fe ( tpa )( NCS ) ₂ ] complex has been investigated by nuclear forward scattering (NFS), nuclear inelastic scattering (NIS), extended X-ray absorption fine structure (EXAFS) spectroscopy, conventional M?ssbauer spectroscopy (MS) and by measurements of the magnetic susceptibility (SQUID). The various measurements consistently show that the transition is complete and abrupt and exhibits a hysteresis between 102 and 110 K. The dependence of the hyperfine parameters of the high-spin (HS) and of the low-spin (LS) phase on temperature is gradual while the effective thickness (determined by the Lamb-M?ssbauer factor f _LM ) shows a step at the transition temperature. This step could be identified clearly because the effective thickness is measured directly by NFS. The Lamb-M?ssbauer factor, the Debye temperature and the mean-square displacement of iron(II) could be determined for the HS and for the LS phase. When comparing the NIS data with the results from density functional theory (DFT), the Fe-N stretching vibrations of both LS and HS phases could be unambiguously identified and the f _LM could be factorized for both phases into a lattice and a molecular part. The structural information from EXAFS and DFT geometry optimization are in reasonable agreement. Received 19 June 2001     

Dynamic triggering of a spin-transition by a pulsed magnetic field

We report the first study of the effect of a high pulsed magnetic field on a spin transition complex in the solid state. The high spin fraction was determined by optical reflectivity. Sizeable effects are observed for the well-known spin transition solid Fe(Phen)₂(NCS)₂. In the hysteresis loop temperature range, an increase in the HS fraction is obtained, with an irreversible (reversible) character in the ascending (descending) branch of the loop. The time dependence of the HS fraction provides information on the kinetics of the spin-crossover process at the spin transition. Received 23 February 1999 and Received in final form 8 June 1999     

Fe2+ spin transition in [Fe(trz)(Htrz)2](BF4) as evidenced by a variable temperature EPR study

The EPR of Fe³⁺ ions has been used for the first time to evidence a low-spin (S=0) to high-spin (S=2) transition of Fe²⁺ ions in an octahedral ferrous complex [Fe(trz)(Htrz)₂](BF₄). The temperature dependence of the intensity of the Fe³⁺ EPR line atg=4.3 reveals a spin transition which occurs for the Fe²⁺ ions, with hysteresis. The transition temperatures areT _c↑=374 K in the warming mode andT _c↓=345 K in the cooling mode. The analysis of the EPR spectral data indicates the presence of a structural phase transition accompanying the spin transition.     

Paramagnetic properties of single-crystal silicon implanted with iron-group transition metals

Samples of single-crystal silicon implanted with iron-group ions are investigated by electron paramagnetic resonance (EPR). The change in relative permittivity μ_r of the silicon layer modified by implanted nickel ions is found. The accumulation kinetics of paramagnetic centers of amorphous regions of silicon implanted with Co, Ni, and Fe are shown to be different. Magnetic hysteresis for both the wide EPR line due to implanted impurities and the EPR line due to dangling chemical silicon bonds is found. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 197–201, March–April, 2008.     

Pressure-induced electron spin transition in the paramagnetic phase of the GdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Heisenberg magnet

The HS → LS spin crossover effect (high-spin → low-spin transition) induced by high pressure in the range 45–53 GPa is observed in trivalent Fe³⁺ ions in the paramagnetic phase of a Gd⁵⁷Fe₃(BO₃)₄ gadolinium iron borate crystal. This effect is studied in high-pressure diamond-anvil cells by two experimental methods using synchrotron radiation: nuclear resonant forward scattering (NFS) and Fe K _β high-resolution x-ray emission spectroscopy (XES). The manifestation of the crossover in the paramagnetic phase, which has no order parameter to distinguish between the HS and LS states, correlates with the optical-gap jump and with the insulator-semiconductor transition in the crystal. Based on a theoretical many-electron model, an explanation of this effect at high pressures is proposed.     

Spin transition in magnesiowüstite in earth's lower mantle

Iron in the major lower mantle (LM) minerals undergoes a high spin (HS) to low spin (LS) transition at relevant pressures (23-135 GPa). Previous failures of standard first principles approaches to describe this phenomenon have hindered its investigation and the clarification of important consequences. Using a rotationally invariant formulation of LDA + U we report a successful study of this transition in low solute concentration magnesiowüstite, (Mg(1-x)Fe(x)(O), (x < 0.2) the second most abundant LM phase. We show that the HS-LS transition goes through an insulating (semiconducting) intermediate mixed spins (MS) state without discontinuous changes in properties, as seen experimentally. We show that the HS state crosses over smoothly to the LS state passing through an insulating MS state where properties change continuously, as seen experimentally.     

Phase transition study in α-Fe2WO6 compound by EPR

The temperature dependence of the EPR spectrum for the α-phase of iron tungstate has been investigated in the temperature range of 40–260 K. At temperatures betweenT ₁ ≈ 250 K andT ₂ ≈ 205 K where the antiferromagnetic phase transition occurs, a relatively narrow EPR line arising from the dominant iron(III) species has emerged, gaining intensity with the temperature increase. Its linewidth temperature evolution could be described by Huber equation, with T_N = 200 K, which is consistent with the peak seen in magnetic susceptibility measurements, while the correspondingg-factor shifts to higher fields reflecting the build-up of internal field emerging from increasing shortrange order in the spin system. At temperatures lower than T₂, a very broad and distorted EPR line with temperature dependentg-factor and linewidth has been observed reflecting the corresponding rise of the magnetic susceptibility below the antiferromagnetic phase transition, presumably arising from magnetic clusters embedded in the antiferromagnetic background.