Mössbauer spectroscopy in molecular magnetism

The aim of this paper is to highlight some selected research activities on molecular magnetic materials using Mössbauer spectroscopy as a technique carried out in our laboratory in recent years. The first part of the present article is devoted to the studies of the various magnetic interactions, metal-to-metal electron-transfer phenomenon, glass transition occurring in molecular magnetic materials, whereas the second part deals with the iron(II) high spin (S = 2)–low spin (S = 0) transition phenomenon occurring in some isoxazole ligand based iron(II) compounds as examples with unusually complicated spin transition behaviour. Also, an example of a dinuclear a spin crossover compound of iron(II) is described, where Mössbauer spectroscopy has most convincingly unraveled the mechanism of the spin transition process. Finally, an example from our most recent studies of spin crossover materials exhibiting both thermal spin crossover and liquid crystalline properties in the same temperature interval near room temperature will be presented.     

Diffusive EPR line width behaviour in two-dimensional Cu(Hippurate)2 4H2O single crystal

X-band EPR measurements were performed at room temperature on layered Cu(Hippurate)₂4H₂O single crystals. Despite the dimeric molecular structure the EPR spectra are characteristic for individual Cu-complexes with square-pyramidal structure and g-factors: g_x=2.045, g_y=2.085 and g_z=2.346. The anticipated zero-field splitting from dimers with S=1 is averaged out by interdimer exchange coupling within the layers. The dimers in adjacent layers are not exchange coupled as we determined from the two-component EPR spectra. Thus, the crystal is an ideal 2D magnetic system and shows a strong spin diffusion effect in the EPR line width. The spin diffusion contribution to the line width is described as P(3cos²Θ−1)² with which is much higher compared to other 2D copper(II) crystals. The background line width is due to dipolar coupling and non-resolved hyperfine structure. Exchange coupling was determined from the exchange narrowing effect as of about 0.1 cm⁻¹.     

EPR Studies of CuCl2-ethanolate Complexes

The molecular and electronic structure of the CuCl₂-complexes with monoethanolamine (MEA) and triethanolamine (TEA), and their dynamical properties in solid and in DMF solutions were discussed on the basis of EPR measurements. Measurements indicate a dimeric structure of CuCl₂-MEA complexes with very weak Cu-Cu coupling. Intradimer superexchange interaction is temperature dependent and decreases with temperature. In CuCl₂-TEA monomeric complexes exist with a significant vibronic effect which is due to a change of d_Z2 admixture to the d x²-y² ground state when temperature is changed.     

EPR of an exchange-coupled,hydrogen-bridged one-dimensional Cu(II) complex containing both octahedral and square pyramidal geometries in the same unit cell

Single-crystal X and Q band EPR of a hydrogen-bridged l-dimensional Cu(II) complex, [Cu(stpy)₂(CH₃COO)₂(H₂O)₂] [CU(stpy)₂(CH₃COO) ₂(H₂O)], containing both octahedral and square pyramidal geometries in the same unit cell, has been studied at 300 K. EPR of powder samples at X band frequencies at 300 K and 77 K show exchange-narrowed resonance. The peak-to-peak linewidths of the signals are 80 G and 85 G, respectively. However, at Q band frequencies it exhibits an axially symmetric spectrum with spin Hamiltonian parameters g_|| = 2.303 and g_⊥ = 2.077, corresponding to an |x² ? y²〉 ground state. Single-crystal X band EPR spectra show a single resonance line for all the orientations, indicating the complex to be in the strong exchange regime. On the other hand, Q band spectra exhibit two lines corresponding to the weak exchange regime. An estimate of the interchain-site exchange coupling constant J′ = 0.0125(3) cm^?1 also reveals weak coupling between the magnetically distinct Cu(II) centres. The ratio of J′/J = 8.25 × 10^?2 is low enough to make the interactions almost l-dimensional, in agreement with X-ray data. EPR linewidth and lineshape analyses also support l-dimensional behaviour of the system.     

EPR of Spin Transitions in Complexes of Cu(hfac)2 with tert-Butylpyrazolylnitroxides

Polymer chain complexes [Cu(hfac)₂L^R] _n exhibit thermally and light-induced magnetic anomalies in many aspects similar to a spin crossover. These compounds attracted significant attention in the field of molecular magnetism and have been extensively studied by electron paramagnetic resonance (EPR) during the last several years. All compounds studied so far were based on copper(II) ions bridged by pyrazolyl-substituted nitronylnitroxides. The present work reports the first EPR study of complexes of Cu(hfac)₂ with tert-butylpyrazolylnitroxides—a new type of nitroxide ligand expected to modify exchange interaction pathways and physical properties of the crystals. The Q-band EPR spectra of three representative novel compounds are principally different from those studied previously, supporting the assumption that the magnetic motif of the compound has changed. Dominant intercluster exchange interactions are now found along the structural polymer chains. This complicates the EPR detection of phase transitions to some extent; however, theoretical modeling of the observed spectral changes allows for unambiguous assignment of different spin states and transitions between them. The magnitudes of intercluster exchange interaction were estimated to be ca. 0.1–1.5 cm^?1 for the studied compounds.     

Induced spin polarization of copper spin 1/2 molecular layers

Thin films of the metal organic molecule bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) (or Cu(CNdpm)₂), (C₂₄H₃₆N₂O₄Cu, Cu(II)), deposited on ferromagnetic Co(111) at 40 K, exhibit a finite electron spin polarization. The spin polarization magnitude and sign for Cu(CNdpm)₂ deposited on Co(111) is coverage dependent, but deviates from the mean field expectations for a simple paramagnet on a ferromagnetic substrate. The spin asymmetry is seen to favor select molecular orbitals, consistent with the predicted single molecule density of states. The overlayer polarization observed indicates a strong influence of the ferromagnetic Co(111) substrate and some extra-molecular magnetic coupling.     

Exchange interaction and spin dynamics in pentanuclear clusters, Cu3Ln2(ClCH2COO)12(H2O)8 (Ln = Nd3+, Sm3+, Pr3+)

New compounds, [Cu₃Ln₂(ClCH₂COO)₁₂(H₂O)₈]·2H₂O with Ln = Nd³⁺ (I), Sm³⁺ (II), Pr³⁺ (III), built up of pentanuclear clusters were synthesized and studied by means of X-ray analysis and electron paramagnetic resonance (EPR). X-ray data show that all compounds are isostructural and the pentanuclear clusteres may be considered as a linear system with alternating Cu(II) and Ln(III) ions: Cu(2)-L¹-Ln-L²-Cu(1)-L²-Ln-L²-Cu(2) with L¹ and L² being bridging fragments and Cu(1) and Cu(2) being structurally nonequivalent copper complexes. EPR studies demonstrate that in the temperature range of 100–293 K the signals due to only one type of the copper complexes are observed in the spectra of I–III. AtT<100 K the spectral temperature dependence is nontrivial. AtT<30 K new signals are detected in the spectra of I and II. The temperature dependence of the EPR spectra is interpreted under the assumption that the parameter of the exchange interaction Cu(2)-Ln considerably exceeds the parameter of the interaction Cu(1)-Ln. EPR spectra are calculated for the fragments of five paramagnetic centers in the frames of the model taking into account the nonequivalence of two copper complexes, short longitudinal and transverse paramagnetic relaxation times of the rare-earth ions at room temperature and the change of the relaxation rates when the temperature decreases. The results of the calculations show that it is possible to obtain information about the interactions in the system on the basis of the analysis of the temperature dependence of the EPR spectra of the central copper complex. The parameter of the isotropic part of the exchange interaction between copper and neodymium ions (for the interaction Cu(2)-Nd) is estimated as about 15 cm⁻¹. A considerable rearrangement of the spin states when the temperature changes is found for all complexes.     

EPR Studies of DOPA–Melanin Complexes with Netilmicin and Cu(II) at Temperatures in the Range of 105–300?K

The application of electron paramagnetic resonance (EPR) spectroscopy in pharmacy of melanin complexes with netilmicin and Cu(II) was presented. The continuous microwave saturation of EPR spectra of DOPA–melanin and the complexes was performed. EPR spectra were measured on an X-band (9.3?GHz) spectrometer at temperatures in the range of 105–300?K. Paramagnetic copper ions decrease the intensity of the EPR lines of melanin’s free radicals. It was found that fast spin–lattice relaxation characterizes DOPA–melanin–Cu(II) complexes. Slow spin–lattice relaxation processes exist in melanin’s paramagnetic centers of DOPA–melanin and DOPA–melanin–netilmicin, [DOPA–melanin–netilmicin]–Cu(II), [DOPA–melanin–Cu(II)]–netilmicin complexes. Spin–lattice relaxation processes are faster at higher temperatures. The homogeneous broadening of EPR lines for melanin complexes was observed. The practical consequences of differences between paramagnetic properties of melanin complexes with netilmicin and the complexes with Cu(II) were discussed.     

Spectral distribution of relaxation times in spin glasses

Recent neutron scattering measurements on spin glasses show that the dynamics of the spin systems can be best described in terms of wide spectral distribution of relaxation times evolving continuously with decreasing temperature but which is devoid of any critical behaviour, either speeding up or slowing down, at any finite temperature including the spin glass “freezing temperature T_sg”. It is argued that the latter temperature itself is dependent on the time constant of measurement for all spin glasses in general; the observed variation with frequency being less pronounced in some systems than others owing to some special characteristics of their spin dynamics such as, for example, the presence of parallel channels of rapid relaxation provided by the Korringa coupling in metallic spin glasses. The neutron scattering measurements presented here enable us to propose plausible forms for the density of relaxation times of the spin system and to show that the logarithmic frequency dependence of the freezing temperature observed in low frequency ac susceptibility measurements follows naturally from a uniform density of relaxation times at these frequencies.     

Quantitative analysis of dinuclear manganese(II) EPR spectra

A quantitative method for the analysis of EPR spectra from dinuclear Mn(II) complexes is presented. The complex [(Me(3)TACN)(2)Mn(II)(2)(mu-OAc)(3)]BPh(4) (1) (Me(3)TACN=N, N('),N(")-trimethyl-1,4,7-triazacyclononane; OAc=acetate(1-); BPh(4)=tetraphenylborate(1-)) was studied with EPR spectroscopy at X- and Q-band frequencies, for both perpendicular and parallel polarizations of the microwave field, and with variable temperature (2-50K). Complex 1 is an antiferromagnetically coupled dimer which shows signals from all excited spin manifolds, S=1 to 5. The spectra were simulated with diagonalization of the full spin Hamiltonian which includes the Zeeman and zero-field splittings of the individual manganese sites within the dimer, the exchange and dipolar coupling between the two manganese sites of the dimer, and the nuclear hyperfine coupling for each manganese ion. All possible transitions for all spin manifolds were simulated, with the intensities determined from the calculated probability of each transition. In addition, the non-uniform broadening of all resonances was quantitatively predicted using a lineshape model based on D- and r-strain. As the temperature is increased from 2K, an 11-line hyperfine pattern characteristic of dinuclear Mn(II) is first observed from the S=3 manifold. D- and r-strain are the dominate broadening effects that determine where the hyperfine pattern will be resolved. A single unique parameter set was found to simulate all spectra arising for all temperatures, microwave frequencies, and microwave modes. The simulations are quantitative, allowing for the first time the determination of species concentrations directly from EPR spectra. Thus, this work describes the first method for the quantitative characterization of EPR spectra of dinuclear manganese centers in model complexes and proteins. The exchange coupling parameter J for complex 1 was determined (J=-1.5+/-0.3 cm(-1); H(ex)=-2JS(1).S(2)) and found to be in agreement with a previous determination from magnetization. The phenomenon of exchange striction was found to be insignificant for 1.     

Observation of complex magnetic behavior in the perovskite rare earth copper oxide systems, R2CuO4

EPR, microwave absorption, and dc magnetization measurements were made on single crystals of the form R₂CuO₄, which are the host compounds for the newly discovered series of electron cuprate superconductors. These measurements reveal two characteristic transition temperatures associated with a novel complex magnetic behavior, including weak ferromagnetism, two sharp peaks in the low field DC magnetization, an unusual anisotropy in the EPR resonance field for R = Gd, and two additional anisotropic microwave absorption modes. The higher characteristic transition temperature, at ≈270K, is attributed to AF ordering of the Cu moments, and the lower, at ≤20K, to a spontaneous canted spin reorientation. An understanding of this magnetic behavior is important in order to ascertain its relationship to possible mechanisms of high temperature superconductivity.     

[Cu2(O COO C-O-N H-O-CH3)4(DMF2)]·4DMF的EPR谱、磁性与电子结构研究

在室温、77K条件下,对·4DMF(1)簇合物的固态和溶液样品进行了EPR谱的测定,获得三套谱图(Ⅰ、Ⅱ、Ⅲ),其分别归属于簇合物中未配对电子的两种形式:(1)类似于自由的单铜离子的未配对电了(Ⅰ、Ⅱ两套谱).(2)双铜未配对电子偶合成的三重态(Ⅲ套谱). 文中用双铜的三重态自旋哈密顿H_S=βHgS+DS_z²+E(S_x²-S_y²)-(2)/3D公式计算三重态EPR谱的参数. 题目化合物(1)与双铜簇合物·4DMF(2)相比较,在配体结构上稍有不同(前者,甲苯胺中的甲基是连接于苯环的间位;而后者,甲基是连接于苯环的对位),由此引起一些磁性参数:有效磁矩μ_eff、磁交换相互作用参数J、相对的电子自旋浓度ρ和EPR谱的超精细结构(h.f.s)参数都有所不同.     

EPR spectra of gable-type copper(II) porphyrin dimers in fluid solution: extraction of exchange interaction in weakly coupled doublet pairs

A comparison between EPR spectra of rigidly linked dicopper porphyrin dimers and those of the corresponding monocopper dimers (copper porphyrin-free base porphyrin dimers) in fluid solution reveals a very weak exchange interaction between the two copper spins. In these dimers, two porphyrin moieties are linked via an aromatic spacer such as benzene, naphthalene or phenanthrene in a gable-type geometry, with a distance of 10–13 Å. Although essentially all the spectra from the monocopper dimers are the same, exhibiting hyperfine (hf) structure due to the copper and nitrogen nuclei, the EPR spectral patterns of the dicopper dimers depend on the spacer molecule. Differences in hf patterns among the dicopper porphyrin dimers are ascribed to isotropic spin—spin coupling, i.e., exchange coupling between the two copper spins. This is because the anisotropic dipole—dipole interaction is averaged out due to random tumbling of the solute molecules in fluid solution. From the line shape analysis, the absolute value of the exchange interaction (|J|) is found to be 4 × 10^?4 cm^?1 ≦|J| < 3 × 10^?3 cm^?1 for the benzene linked dicopper dimer (Cu—Bz—Cu) whereas |J| ～ 1 × 10^?4cm^?1 for the other two dimers (Cu—Np—Cu and Cu—Pn—Cu). These values are comparable with or much smaller than the dipole—dipole coupling, which is estimated as about 1–3 × 10^?3 cm^?1 from the centre-to-centre distance. Since Cu—Bz—Cu shows a significantly larger |J| than Cu—Pn—Cu, despite a slightly longer centre-to-centre distance, and since no correlation could be obtained between |J| and the separation of the two copper atoms, it is likely that the interaction via spacer molecules is dominant between the two halves.     

Electronic Studies of Copper(II) Complexes of Amino Acids. III. EPR Spectra of Some Vitamin B6 Schiff Base Analogs

Schiff base coordination compounds of amino acids are good models to study the transamination reaction^2,3 of vitamin B₆. Several studies^4-6 have focused on the preparation, characterization and spectra study of these Schiff base coordination compounds, represented schematically in Figure 1, where R has been varied. In our continued studies of Cu(II) coordination compounds of amino acids, we have prepared a series of compounds with alanine (R=CH₃) and either a 4 or 5 substituent on the ring (X=H, OH, NO₂, Cl). In order to obtain as many of the EPR magnetic parameters as possible⁷, we prepared solid solutions in Zn(II) matrices with a Zn(II) to Cu(II) ratio of about 95:5. In this fashion we were able to reduce the dipole coupling and to calculate the [sgrave] molecular orbital coefficients for this important new series of compounds.     

Spectroscopic Studies of Oxygen-Bridged Copper (II) Cluster Complexes; (I) Dimeric Copper (II) Complexes of 2-Aminopyridine and Pentane-2,4-Dionate

X-band E.P.R and also the far infrared spectra of alkoxy-bridged dimeric copper (11) complexes of 2-aminopyridime and pentane-2, 4-dionate were recorded and the two sets of data thus obtained have been correlated.

The E.P.R spectra were analysed in terms of an axial (S=1) spin Hamiltonian. Zero-field splitting parameter (D) was calculated for each complex and an attempt was made in order to correlate the obtained values with the magnetic coupling constants (J) of some compounds with analogous structures.

An assignment has been made of the bands related to the central Cu202 bridging skeleton and the observed similarity in the frequency magnitude of a strongly CuOCu angle dependent mode has been proposed to arise from nearly equal angles in the seri of complexes.

The correlative results indicated in the above have therefore enabled the identification of a ferromagnetic exchange mechanism in the seri of complexes with J values larger than 242.5 cm-1.     

EPR studies of weakly coupled oxomolybdenum (V) and low-spin iron (III) porphyrin centers

Novel compounds containing twoS=1/2 coupled spin centers (Mo(V) and low spin Fe(III) have been investigated in detail by X- and Q-band EPR spectroscopy, spectral simulation and molecular modelling calculations. For one system with a Mo?Fe distance of ≈9.4 Å the dominant dipolar coupling allows distinction among structures that are consistent with molecular modelling calculations. For the second system with a Mo?Fe of ≈ 7.9 Å the exchange interaction is dominant (0.5 <J < 3.0 GHz). These coupled systems are preliminary benchmarks for using EPR to investigate the Mo?Fe interaction in sulfite oxidase.     

Characterization of Phyllanthus amarus herb by inductively coupled plasma mass spectrometric (ICP-MS) analysis,optical absorption and electron paramagnetic resonance (EPR) spectroscopic methods

A powdered sample of Phyllanthus amarus herb of Kadapa district of Andhra Pradesh, India, is used in the present study. ICP-MS analysis indicates that copper is present in higher concentration when compared to other elements. Although the Pb is toxic, it is within the permissible limit. The evaluated soil and herb physico-chemical parameters indicate that the sample is acidic in nature in comparison with the soil. An EPR study on powdered sample confirms the presence of Fe(III), Mn(II) and Cu(II). Optical absorption spectrum indicates that Fe(III) impurity is present in octahedral structure whereas Cu(II) is present in rhombically distorted octahedral environment. MIR results are due to carbonate fundamentals.     

Electron spin relaxation in pseudo-Jahn-Teller low-symmetry Cu(II) complexes in diaqua(L-aspartate)Zn(II).H(2)O crystals.

Low-temperature (4-55 K) pulsed EPR measurements were performed with the magnetic field directed along the z-axis of the g-factor of the low-symmetry octahedral complex [(63)Cu(L-aspartate)(2)(H2O)2] undergoing dynamic Jahn-Teller effect in diaqua(L-aspartate)Zn(II) hydrate single crystals. Spin-lattice relaxation time T(1) and phase memory time T(M) were determined by the electron spin echo (ESE) method. The relaxation rate 1/T(1) increases strongly over 5 decades in the temperature range 4-55 K. Various processes and mechanisms of T(1)-relaxation are discussed, and it is shown that the relaxation is governed mainly by Raman relaxation processes with the Debye temperature Theta(D)=204 K, with a detectable contribution from disorder in the doped Cu(2+) ions system below 12 K. An analytical approximation of the transport integral I(8) is given in temperature range T=0.025-10Theta(D) and applied for computer fitting procedures. Since the Jahn-Teller distorted configurations differ strongly in energy (delta(12)=240 cm(-1)), there is no influence of the classical vibronic dynamics mechanism on T(1). Dephasing of the ESE (phase relaxation) is governed by instantaneous diffusion and spectral diffusion below 20 K with resulting rigid lattice value 1/T(0)(M)=1.88 MHz. Above this temperature the relaxation rate 1/T(M) increases upon heating due to two mechanisms. The first is the phonon-controlled excitation to the first excited vibronic level of energy Delta=243 cm(-1), with subsequent tunneling to the neighbor potential well. This vibronic-type dynamics also produces a temperature-dependent broadening of lines in the ESEEM spectra. The second mechanism is produced by the spin-lattice relaxation. The increase in T(M) is described in terms of the spin packets forming inhomogeneously broadened EPR lines.     

Magnetic properties and EPR spectra of [Cu(L-arginine)2](NO3)2·3H2O

Magnetic and EPR data have been collected for complex [Cu(L-Arg)₂](NO₃)₂·3H₂O (Arg=arginine). Magnetic susceptibility χ in the temperature range 2-160 K, and a magnetization isotherm at T=2.29(1) K with magnetic fields between 0 and 9 T were measured. The observed variation of χT with T indicates predominant antiferromagnetic interactions between Cu(II) ions coupled in 1D chains along the b axis. Fitting a molecular field model to the susceptibility data allows to evaluate g=2.10(1) for the average g-factor and J=−0.42(6) cm⁻¹ for the nearest neighbor exchange coupling (defined as H_ex=-∑J_ijS_i·S_j). This coupling is assigned to syn-anti equatorial-apical carboxylate bridges connecting Cu(II) ion neighbors at 5.682 Å, with a total bond length of 6.989 Å and is consistent with the magnetization isotherm results. It is discussed and compared with couplings observed in other compounds with similar exchange bridges. EPR spectra at 9.77 were obtained in powder samples and at 9.77 and at 34.1 GHz in the three orthogonal planes of single crystals. At both microwave frequencies, and for all magnetic field orientations a single signal arising from the collapse due to exchange interaction of resonances corresponding to two rotated Cu(II) sites is observed. From the EPR results the molecular g-tensors corresponding to the two copper sites in the unit cell were evaluated, allowing an estimated lower limit |J |>0.1 cm⁻¹ for the exchange interaction between Cu(II) neighbors, consistent with the magnetic measurements. The observed angular variation of the line width is attributed to dipolar coupling between Cu(II) ions in the lattice.