Nuclear inelastic scattering studies on a dinuclear iron(II) spin crossover complex

The vibrational properties of the (high-spin)-(high-spin) and the (high-spin)- (low-spin) states of the dinuclear Fe(II) spin crossover complex[{Fe(L-N₄Me₂)}₂(BiBzIm)](ClO₄)₂·2EtCN¹ have been studied by means of nuclear inelastic scattering. At a temperature of 80 K typical low spin marker bands are detected in the region around 400 cm^?1, these bands almost completely disappear after increasing temperature to 190 K. Corresponding density functional theory calculations using the functional B3LYP* and the basis set CEP-31G reproduce the experimental data and thus allow a deeper understanding of the vibrational properties of dinuclear Fe(II) spin crossover complexes.     

Experimental evidence of the vibrational coupling of nearest neighbours in 1D spin crossover polymers of rigid bridging ligands

The nuclear inelastic scattering signatures of the low spin centres of the methanosulphonate, tosylate and perchlorate salts of the spin crossover polymer ([Fe(II)(4-amino-1,2,4-triazole)₃]⁺²) _n have been compared for the pure low-spin phase, for the mixed high-spin and low-spin phases, as well as for Zn(II) diluted samples. Within this series a change in the spectral pattern in the 320–500 cm^?1 region is observed involving the decrease of the intensities of a band at ～320 cm^?1 and those over 400 cm^?1 as the molar fraction of the low-spin centres decreases. On the basis of the DFT calculations (B3LYP/CEP-31G) this effect is interpreted in terms of vibrational coupling of the iron centres of the same spin.     

Study on the spin crossover transition and glass transition for Fe(II) complex film, [Fe(II)(H-triazole) 3 ]@Nafion, by means of M?ssbauer spectroscopy

[Fe(II)(H-trz)₃]@Nafion (trz = triazole) is a transparent spin crossover complex film, where the spin crossover transition between the low-spin (S = 0) and the high-spin (S = 2) states takes place between 225?K and 300?K. In this film, two doublets corresponding to the low-spin and high-spin states were observed in the ⁵⁷Fe M?ssbauer spectra, reflecting the spin crossover transition. From the analysis of ⁵⁷Fe M?ssbauer spectra, the Debye temperatures of the low-spin and high-spin sites were estimated at 185?K and 176?K, respectively, in the temperature range between 10?K and 150?K. In this film, the total intensity of the M?ssbauer spectra corresponding to the low-spin and high-spin sites drastically decreases above 200?K, reflecting the glass transition of Nafion, where the lattice vibration of [Fe(H-trz)₃] $_{\rm n}^{\,\,\rm 2n+}$ is softened just as in solution due to micro-Brown motion of the segment of Nafion polymer membrane.     

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.     

Mössbauer,magnetic susceptibility,EPR, and EXAFS investigations of the vibrationally-induced low-spin/high-spin transition in a biomimetic Fe(III) complex

Magnetic susceptibility measurements from 2 to 520 K, Mössbauer measurements from 1.2 to 450 K, and EPR measurements at 10 K have been performed on the monomeric Fe^III complex (1,4,7-tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triaza-cyclononan)Fe. The complex exhibits a low-spin/high-spin transition at temperatures above 250 K. This behavior is quantitatively explained on the basis of a crystal-field model, which explicitly includes the vibrational properties of iron ligands. The EPR spectrum at 10 K yields a pure Fe^III low-spin signal withg values 2.58(5), 2.12(5), 1.45(5). The values are consistently described by a crystal-field model, which explicitly includes spin-orbit coupling within the t_2g subspace. The temperature dependence of the quadrupole splitting indicates a phase transition at approximately 100 K. The existence of the phase transition is corroborated by the temperature dependence of the effective thickness. The observation of only one quadrupole doublet up to 450 K indicates that the relaxation time between the high-spin and the low-spin configurations is shorter than the quadrupole precession time. X-ray structure analysis on single crystals at RT and temperature-dependent EXAFS investigation of powder material between 30 and 200 K indicate that the observed phase transition induces only changes of bond angles, while the low-spin/high-spin transition most likely induces changes of metal-ligand bond distances.     

Spin conversion detected by Mössbauer spectroscopy and μSR on a 1D FeII paramagnetic chain

While magnetic properties of the 1D chain [Fe(hyetrz)₃](4-bromophenylsulfonate)₂ investigated over the temperature range from 300 K to 2 K show paramagnetic behavior, detailed ⁵⁷Fe Mössbauer and muon spin relaxation measurements reveal an unexpected spin conversion. Approximately ~14 % of the high-spin ions are found to convert to the low-spin state with a transition temperature T _1/2?~?120 K.     

Site-selective detection of vibrational modes of an iron atom in a trinuclear complex

Nuclear inelastic scattering (NIS) experiments on the trinuclear complex [⁵⁷Fe{L-N₄(CH₂Fc)₂} (CH₃CN)₂](ClO₄)₂ have been performed. The octahedral iron ion in the complex was labelled with ⁵⁷Fe and thereby exclusively the vibrational modes of this iron ion have been detected with NIS. The analysis of nuclear forward scattering (NFS) data yields a ferrous low-spin state for the ⁵⁷Fe labelled iron ion. The simulation of the partial density of states (pDOS) for the octahedral low-spin iron(II) ion of the complex by density functional theory (DFT) calculations is in excellent agreement with the experimental pDOS of the complex determined from the NIS data obtained at 80 K. Thereby it was possible to assign almost each of the experimentally observed NIS bands to the corresponding molecular vibrational modes.     

Mössbauer spectroscopic study of the thermal spin crossover in [Fe(II)(isoxazole)6](ClO4)2

The ⁵⁷Fe Mössbauer spectroscopy of mononuclear [Fe(II)(isoxazole)₆](ClO₄)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 Mössbauer 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(↓)=223 and T_C(↑)=213 K occurring in the reverse order in comparison to those observed in SQUID observation and many other spin transition compounds. The compound has three high-spin Fe(II) sites at the highest temperature of study of which two undergo spin transitions. The compound seems to undergo a structural phase transition around the spin transition temperature, which plays a significant role in the spin crossover behaviour as well as the magnetic properties of the compound at temperatures below T_C. The present study reveals an increase in high-spin fraction upon heating in the temperature range below T_C, and an explanation is provided.     

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.     

High-pressure magnetic properties and <Emphasis Type="Italic">P-T</Emphasis> phase diagram of iron borate

The high-pressure magnetic states of iron borate ⁵⁷FeBO₃ single-crystal and powder samples have been investigated in diamond anvil cells by nuclear forward scattering (NFS) of synchrotron radiation at different temperatures. In the low-pressure (0 < P < 46 GPa) antiferromagnetic phase, an increase of the Neél temperature from 350 to 595 K induced by pressure was found. At pressures 46–49 GPa, a transition from the antiferromagnetic to a new magnetic state with a weak magnetic moment (magnetic collapse) was discovered. It is attributed to the electronic transition in Fe³⁺ ions from the high-spin 3d⁵ (S = 5/2, ⁶A_1g) to the low-spin (S = 1/2, ²T_2g) state (spin crossover) due to the insulator-semiconductor-type transition with extensive suppression of strong d-d electron correlations. At low temperatures, NFS spectra of the high-pressure phase indicate magnetic correlations in the low-spin system with a magnetic ordering temperature of about 50 K. A tentative magnetic P-T phase diagram of FeBO₃ is proposed. An important feature of this diagram is the presence of two triple points where magnetic and paramagnetic phases of the high-spin and low-spin states coexist.     

Intermediate electronic relaxation betweenS=3/2 andS=1/2 states in Fe(J-mph)NO with a jäger-type ligand J-mph

The incomplete spin transition between the low-spin (LS) (S=1/2) and the intermediate-spin (IS) (S=3/2) states in the iron (III) complex Fe(J-mph)NO (mph=4-methyl-o-phenylene), centered atT _c≈212 K, has been studied with⁵⁷Fe Mössbauer spectroscopy and magnetic susceptibility measurements between 80 K and 320 K. The lineshape of the Mössbauer spectra is well reproduced by a two state stochastic relaxation model resulting in values of about 2·10⁶ s^?1 to 7·10⁶ s^?1 for the IS→LS transition rate constantk _IL. The kinetics of this spin transition can be described by an Arrhenius equation yielding activation energiesE _IL=1.1 (2) kJ/mol andE _LI=6.1 (2) kJ/mol for the IS→LS and LS→IS conversion, respectively.     

Temperature dependence of the spin state of a Co3+ Ion in RCoO3 (R = La,Gd) cobaltites

Changes in the spin state of Co³⁺ ions in LaCoO₃ and GdCoO₃ compounds are studied through the use of the temperature dependence of the magnetic susceptibility and the modified crystal field theory. It is shown that the spin subsystem of Co³⁺ ions in LaCoO₃ and GdCoO₃ undergoes the spin-crossover type transition between the high-spin (S = 2) and low-spin (S = 0) states without any contribution of the intermediate-spin state (S = 1).     

High-spin-low-spin transition in magnesiowüstite (Mg<Subscript>0.75</Subscript>,Fe<Subscript>0.25</Subscript>)O at high pressures under hydrostatic conditions

The spin states of Fe²⁺ ions in (Mg_0.75,Fe_0.25)O magnesiowüstite crystals at hydrostatic pressures up to 90 GPa created in a diamond-anvil cell with helium as a pressure-transmitting medium have been investi-gated by transmission and synchrotron Mössbauer spectroscopy at room temperature. An electron transition from the high-spin (HS) state to the low-spin (LS) state (HS-LS crossover) has been observed in the pressure range of 55–70 GPa. The true HS-LS transition occurs in a narrow pressure range and the extension of the electron transition to ～15 GPa is attributed to the effect of the nearest environment and to thermal fluctuations between the high-spin and low-spin states at finite temperatures. It has been found that the lowest pressure at which the electron HS-LS transition can occur in the Mg_{1 ? x} Fe _x system is 50–55 GPa.     

Optimization of the conditions of synchrotron Mössbauer experiment for studying electronic transitions at high pressures by the example of (Mg, Fe)O magnesiowustite

The effect of the experimental conditions on the shape of the nuclear resonant forward scattering (NFS) from (Mg_0.75Fe_0.25)O magnesiowustite has been studied at high pressures up to 100 GPa in diamond anvil cells by the method of the NFS of synchrotron radiation from the Fe-57 nuclei at room temperature. The behavior of the system in the electronic transition of the Fe²⁺ ion from the high-spin to low-spin state (spin crossover) near 62 GPa is analyzed as a function of the sample thickness, degree of nonhydrostaticity, and focusing and collimation conditions of a synchrotron beam. It is found that the inclusion of dynamical beats associated with the sample thickness is very important in the approximation of the experimental NFS spectra. It is shown that the electronic transition occurs in a much narrower pressure range (±6 GPa) rather than in a broad range as erroneously follows from experiments with thick samples under strongly nonhydrostatic conditions.     

2-D electron spin transient nutation spectroscopy of Lanthanoid ion Eu2+(8S7/2) in a CaF2 single crystal on the basis of FT-pulsed electron spin resonance spectroscopy: Transition moment spectroscopy

This work demonstrates the usefulness of pulsed electron spin resonance (ESR)-based two-dimensional electron spin transient nutation (2-D ESN) spectroscopy for complete assignments of complicated fine-structure hyperfine ESR spectra including hyperfine forbidden transitions from electronic and nuclear high-spin systems. The 2-D ESN spectroscopy is termed transition moment spectroscopy as spectra are acquired as a function of transition moment instead of transition energy used in conventional spectroscopy. We have applied the novel spectroscopic technique to Eu²⁺ ion (S=7/2,I=5/2), which has two isotopes (¹⁵¹Eu [47.9%] and¹⁵³Eu [52.1%]), in a CaF₂ single crystal as a model system. We have completely identified the complicated fine-structure hyperfine ESR spectra by invoking the spectral simulation of the 2-D ESN spectra on the basis of transition moment analyses. The analyses are based on exact numerical calculations of the transition moments as well as a perturbation-based analytical approach combined with reduced rotation matrices for the nuclear part of the transition moment. This is the first example of the spectral simulation for 2-D ESN spectra including the hyperfine allowed and forbidden transitions in high-spin systems. In addition, we have made simulation of the fine-structure forbidden transitions, which reproduces the angular variations of the observed spectra at liquid helium temperatures.     

Anisotropic nuclear inelastic scattering of an iron(II) molecular crystal

Nuclear inelastic scattering (NIS) spectra were recorded for a monocrystal of the spin-crossover complex [Fe(tptMetame)] (ClO (4))(2) (tptMetame = 1,1,1-tris([N-(2-pyridylmethyl)-N-methylamino]-methyl)ethane) at T = 30 K (low-spin state) and at room temperature (high-spin state) for different crystal orientations. The high energy resolution (0.65 meV) allowed us to resolve individual molecular vibrations which were unambiguously identified by density functional calculations. From the NIS spectra for the first time the angular-resolved iron-partial density of phonon states (PDOS) was extracted. The PDOS corroborates a vibrational entropy difference as driving force of the spin transition.     

The adsorption of ammonia on a Fe(110) single crystal surface studied by high resolution electron energy loss spectroscopy (EELS)

EELS spectra of ammonia adsorbed on a Fe(110) single crystal surface at 120 K reveal four different molecular adsorption states:1. At very low exposures (0.05 L) three vibrational losses at 345 cm^?1, 1170 and 3310 cm^?1 are observed which are attributed to the symmetric Fe-N stretching-, N-H₃ deformation and N-H₃ stretching modes of chemisorbed molecular ammonia, respectively. The observation of only three vibrational losses indicates an adsorption complex of high symmetry (C_3v).2. Further exposures up to 0.5 L cause the appearance of additional losses at 1450 cm^?1, 1640 cm^?1 and 3370 cm^?1. The latter two are interpreted as the degenerate NH₃ deformation and - stretching modes of molecularly adsorbed NH₃. The 1450 cm^?1 loss is a combination of the losses at 345 cm^?1 and 1105 cm^?1. The observation of 5 vibrational losses is consistent with an adsorption complex of C_s symmetry.3. In the exposure range from 0.5 to 2 L adsorption of molecular ammonia in a second layer is observed. This phase is characterized by a symmetric deformation mode at 1190 cm^?1 and by two additional very intense modes at 160 cm^?1 and 350 cm^?1 which are due to rotational and translational modes.4. Exposures above 2 L cause multilayer condensation of ammonia characterized by translational and rotational bands at 190 cm^?1, 415 cm^?1 and 520 cm^?1, and a symmetric deformation mode at 1090 cm^?1. A broad loss feature around 3300 cm^?1 is attributed to hydrogen bonding in the condensed layer.Thermal processing of a Fe(110) surface ammonia covered at 120 K leads to decomposition of the ammonia into hydrogen and nitrogen above 260 K. No vibrational modes due to adsorbed NH or HN₂ species were detected.     

Photoinduced phase transition accompanied with the changes in magnetic properties

Recently, many studies have been started in search for materials which show a photoinduced phase transition (PIPT). In this work, we review two systems as typical examples of PIPT accompanied with changes in magnetic characteristics; (1) organo-metal complex [Fe(2-pic)₃]Cl₂ EtOH (2-pic = 2-amino-methyl-pyridine) and (2) III-V based magnetic semiconductors (In_1-x , Mn _x )As. In the former case, we show several nonlinear characteristics in dynamical process of photoinduced spin state transition from low-spin to high-spin states. In the latter one, photocarrier-induced ferromagnetic order has been observed by both magnetic and transport measurements.     

Terahertz Cyclotron Photoconductivity in a Highly Unbalanced Two-Dimensional Electron–Hole System

The magnetic properties of the α-Fe₂O₃ hematite at a high hydrostatic pressure have been studied by synchrotron Mössbauer spectroscopy (nuclear forward scattering (NFS)) on iron nuclei. Time-domain NFS spectra of hematite have been measured in a diamond anvil cell in the pressure range of 0–72 GPa and the temperature range of 36–300 K in order to study the magnetic properties at a phase transition near a critical pressure of ~50 GPa. In addition, Raman spectra at room temperature have been studied in the pressure range of 0–77 GPa. Neon has been used as a pressure-transmitting medium. The appearance of an intermediate electronic state has been revealed at a pressure of ~48 GPa. This state is probably related to the spin crossover in Fe³⁺ ions at their transition from the high-spin state (HS, S = 5/2) to a low-spin one (LS, S = 1/2). It has been found that the transient pressure range of the HS–LS crossover is extended from 48 to 55 GPa and is almost independent of the temperature. This surprising result differs fundamentally from other cases of the spin crossover in Fe³⁺ ions observed in other crystals based on iron oxides. The transition region of spin crossover appears because of thermal fluctuations between HS and LS states in the critical pressure range and is significantly narrowed at cooling because of the suppression of thermal excitations. The magnetic P–T phase diagram of α-Fe₂O₃ at high pressures and low temperatures in the spin crossover region has been constructed according to the results of measurements.     

The laser-induced fluorescence spectroscopy of gold monoxide: B2Σ−－X2Π3/2 transition

The electronic spectrum of the gaseous gold monoxide molecule has been investigated in the range of 16000－18500?cm^?1 using laser induced fluorescence spectroscopy and single vibronic level emission spectra. Five rotationally resolved vibronic bands are observed and assigned to the transitions B²Σ^? (v'?=?0－4) －X²п_3/2 (v''?=?0), in which the 0－0 transition is observed for the first time. The molecular constants of the excited state B²Σ^? are obtained by a rotational analysis of the spectra. The spin-orbit coupling constant and the vibrational constants of the ground state X²п_i are determined with the accuracy improved by one order of magnitude. The lifetimes of most observed bands are also measured for the first time.