Synthesis, Characterization and Reactivity Study of a New Penta-Coordinated Mn(II) Complex

A penta-coordinated Mn(II) compound [dqpMnCl₂] (1) (dqp = 2,6-di-(8-quinoline-yl)-pyridine) has been synthesized and its X-ray crystallographic structure is reported here. Magnetic susceptibility measurements confirmed a high-spin Mn(II) (S = 5/2) center in 1. The X-band EPR spectrum of 1 in dimethylformamide solution exhibits widely distributed transitions in the spectral range from 0 to 700 mT with particularly well-resolved hyperfine lines due to the ⁵⁵Mn (I = 5/2) nucleus. The abundance of highly resolved transition lines in the spectrum facilitated the electron paramagnetic resonance spectral simulation which revealed large zero-field splitting and g-anisotropies. When dissolved, 1 exists in equilibrium with a hexa-coordinated species, the latter probably resulting from disassociation of one chlorido-ligand allowing ligation of two solvent molecules. The redox behavior of 1 was studied and was compared to that of a structural analog for which water oxidation in the presence of a chemical oxidant has been shown. The results from water oxidation trials of 1 are discussed.     

Trovacenyl-based organometallic triradicals: Spin frustration, competing interactions and redox splitting

Two new triradicals based on trovacene [η⁷-tropylium)vanadium(η⁵-cyclopentadienyl)], 1,3,5-tri([5]trovacenyl) benzene4 and 1,3,5-tri([5]trovacenyl)-6-methoxybenzene5 were prepared and their magnetic properties were studied by continuous-wave X-band electron paramagnetic resonance (EPR) spectroscopy and by temperature-dependent magnetic susceptometry. The EPR spectra of4 and5 in liquid toluene solution demonstrate that the three unpaired electrons localized on the vanadium atoms interact with each other in both complexes. The data from magnetic susceptometry revealed that the electron spins in both triradicals are antiferromagnetically coupled despite themeta-phenylene bridge. The exchange coupling constants are equal in the C₃-symmetrical triradical4 (J=J′=?0.68 cm^?1), which leads to a twofold degenerate spin ground state (spin frustration). The symmetry lowering by methoxy substitution of the benzene spacer in5 results in the effect of c ompeting interactions (J=?1.83 cm^?1 andJ′=?2.38 cm^?1). In addition to magnetocommunication, the effect of ring substitution on electrocommunication is also discernable. It manifests itself indisparate redox splittings δE _1/2 (0/?, ?/2?) and δE _1/2 (?/2?, 2?/3?) for5, while these parameters are equal for the C₃-symmetrical trinuclear complex4.     

Study on spin configuration in photoresponsive iron mixed-valence complexes by Mössbauer spectroscopy

We have investigated magnetic properties in a series of photoresponsive dithiooxalato (dto)-bridged iron mixed-valence complexes, (SP-R)[Fe^IIFe^III(dto)₃] (SP-R = R-substituted pyridospiropyran cation; R = Me, Et, and Pr; abbreviated as 1 ^Me, 1 ^Et, and 1 ^Pr, respectively). As for our previous reports, 1 ^Me and 1 ^Et show two-step succeeding ferromagnetic transitions at T _C?=?25 & 8 K and 22 & 5 K, respectively. However, 1 ^Et has no hysteresis in the magnetic susceptibility, while 1 ^Me undergoes the charge transfer phase transition with thermal hysteresis around 75 K. To elucidate the two-step transitions of them, we measured ⁵⁷Fe Mössbauer spectra of 1 ^Et. The spectra of Fe^II (S?=?2) and Fe^III (S?=?1/2) in the HTP were observed in the magnetically ordered state as well as the paramagnetic state, and revealed that only HTP exists in a temperature range up to 5 K. The result is consistent with that of 1 ^Pr, where one ferromagnetic phase transition occurs at T _C?=?10 K. ⁵⁷Fe Mössbauer spectroscopy is useful to clarify the origin of the succeeding magnetic transition for these systems.     

The influence of disorder on magnetocaloric effect and the order of transition in ferromagnetic manganite (La1−x Nd x )2/3(Ca1−y Sr y )1/3MnO3

Magnetocaloric effect and order of transition in (La_1?x Nd _x )_2/3(Ca_1?y Sr _y )_1/3MnO₃, prepared by conventional solid-state reaction, have been investigated. Using Banerjee criterion, we demonstrate first-order transition for (J1) and (J2 ) as well as second-order transition for (J3 ), (J4 ), and (J5 ) samples. The ΔS _M ^max is ranging between 9.18 Jkg^?1 K^?1 and 4.87 when Nd and Sr content changes leading to relative cooling power (RCP) varying between 330 and 229.35 J/kg. Both ΔS _M ^max and the RCP are found sensitive to the disorder σ ². The universal behavior obtained from ΔS variation curves confirmed the first-order transition for (J1) and (J2 ) samples and second-order transition for (J3), (J4), and (J5 ) samples obtained by Banerjee criterion. All samples with second-order phase transition exhibit inhomogeneous character estimated from local exponent n.     

Phase diagram of antiferromagnetic cobalt fluoride

The H-T phase diagram of antiferromagnetic cobalt fluoride in an external magnetic field H perpendicular to the easy magnetization axis A is completed and used to construct a phase diagram in the variables H _z and H _y . In this diagram, the lines corresponding to second-order phase transitions (between an angular phase and a phase with antiferromagnetic vector I ⊥ A) begin and end in fields of a spin-flip transition (i.e., in an exchange field). A peculiarity of these lines of phase transitions is that each of them has two tricritical points at which this line of second-order phase transitions transforms into a line of first-order phase transitions. A critical angle between the direction of the external magnetic field and the basal plane within which the first-order phase transition takes place is determined.     

Behavior of Short Nitroxide Biradical in Room Temperature Ionic Liquids

The intramolecular electron spin exchange in short nitroxide biradical O=S(OR₆)₂ (I), where OR₆ is 1-oxyl-2,2,6,6-tetramethyl-4-oxypiperidine, dissolved in the room temperature ionic liquids (RTILs) 1-octyl-3-methylimidazolium hexafluorophosphate (omimPF₆), 1-octyl-3-methylimidazolium tetrafluoroborate (omimBF₄), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF₄), and 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF₄) has been studied by electron paramagnetic resonance (EPR) spectroscopy as a function of temperature. Temperature variations of the isotropic nitrogen hyperfine splitting constant a were measured from EPR spectra. Thermodynamic parameters of the conformational rearrangements were calculated and compared with literature data. These intramolecular movements in rather rigid short-chain biradical I dissolved in four different RTILs are described well by the Debye–Stokes–Einstein law. Unrestricted density-functional-theory calculations of the geometry and electronic structure of the biradical were carried out using the ORCA program package, and showed that the O=S< group is available for the interaction with anions and cations of RTIL. The possible mechanism of such conformational transitions in biradical I in RTIL is discussed.     

Rotation of the plane of polarization and linear birefringence of sound in hematite below the morin point

The linear antiferromagnetic birefringence of sound in hematite (α-Fe₂O₃) residing in the collinear easy-axis phase (L ‖ C ₃) below the Morin point is experimentally studied. The plane of polarization of a linearly polarized transverse acoustic wave propagating along the trigonal axis C ₃ of a hematite crystal placed in a magnetic field H applied in the basal plane (H ⊥ C ₃, 3.5 ≤ H ≤ 15 kOe) is found to rotate after a temperature-driven orientational phase transition to the easy-axis state. The angle of rotation exhibits a 180° angular dependence on the direction of the magnetic field in the basal plane and varies from zero to ～π/2. Numerical estimates suggest that the conditions necessary for rotation of the plane of polarization through appreciable angles (～π/2) can be satisfied in the easy-axis phase at orientational phase transition temperatures close to the Morin point, which actually takes place in the fields employed. The results obtained are described sufficiently well by the theory of linear antiferromagnetic birefringence of sound (E.A. Turov) and confirm its main conclusions.     

Influence of the kinematical constraints on the transverse momentum correlation features

The influence of the kinematical constraints on the transverse momentum correlation features in multiparticle processes is studied by means of thedN/(d r ₁ d r ₂) distribution,r ₁ andr ₂ being the transverse momenta of the particles entering in each pair. Using a limited transverse momentum phase space we obtain for high energy reactions a simple analytical expression fordN/(d r ₁ d r ₂). This expression, similar to a phenomenological parametrization proposed for analyzing¯pp annihilation data, served to define a correlation parameter, the non vanishing value of which is due to the energy-momentum conservation constraints.     

First-order phase transition from an antiferromagnetic ferroelectric to a cycloidal multiferroic with weak ferromagnetism during the joint action of applied magnetic and electric fields

The thermodynamics of the phase transition in a perovskite-like multiferroic, in which an antiferromagnetic ferroelectric transforms into a new magnetic state where a spiral spin structure and weak ferromagnetism can coexist in applied magnetic field H, is described. This state forms as a result of a first-order phase transition at a certain temperature (below Néel temperature T _N ), where a helicoidal magnetic structure appears due to the Dzyaloshinskii-Moriya effect. In this case, the axes of electric polarization and the helicoid of magnetic moments are mutually perpendicular and lie in the ab plane, which is normal to principal axis c. Additional electric polarization p, which decreases the total polarization of the ferroelectric P, appears in the ab plane. The effect of applied magnetic and electric fields on the properties of a multiferroic with a helicoidal magnetic structure is described. An alternating electric field is shown to cause a field-linear change in magnetic moment m, whose sign is opposite to the sign of the change of electric field E. The detected hysteretic phenomena that determine the temperature ranges of overheating and supercooling of each phase are explained. A comparison with the experimental data is performed.     

Atomic-vacancy ordering in the lowest tungsten carbide W2C

Atomic-vacancy ordering in the lowest tungsten carbide W₂C with an L′3-type basic hexagonal structure has been studied by neutron diffraction and X-ray diffraction. In the temperature range 2700–1370 K, the only ordered phase of the lowest tungsten carbide is shown to be the trigonal ?-W₂C phase (space group P $\overline 3 $ 1m). This trigonal ?-W₂C phase is found to form via a disorder-order phase transition channel, which includes three superstructure vectors (k ₁₅ ⁽¹⁾ , k ₁₅ ⁽²⁾ , k ₁₇ ⁽¹⁾ ) of two Lifshitz stars ({k ₁₅}, {k ₁₇}, and to be described by two long-range order parameters (η₁₅, η₁₇). The distribution function of carbon atoms in the trigonal ?-W₂C superstructure is calculated, and the corresponding region of the allowable values of the long-range order parameters η₁₅ and η₁₇ is found. Symmetry analysis of other possible superstructures of the lowest tungsten carbide W₂C is performed, and the physically acceptable sequence of phase transformations in W₂C is determined.     

Spin-frustrated antiferromagnets based on <Emphasis Type="Italic">BEDT-TTF</Emphasis> and manganese dicyanamide complexes

The magnetic properties of new radical cation salts (BEDT-TTF)₂[CuMn(dca)₄] (I) and (BEDT-TTF)₂[Mn(dca)₃] (II) [where BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene and dca = N(CN₂)] are investigated using superconducting quantum interference device (SQUID) magnetometry and electron paramagnetic resonance (EPR) spectroscopy. It is established that, at temperatures below 25 K, both salts are characterized by antiferromagnetic deviations from the paramagnetic behavior. The Weiss constants for compounds I and II are determined to be ?5 and ?10 K, respectively. The corresponding correlations in the structure of compound I are short-range correlations and do not lead to a change in the effective spin equal to 5/2. It is found that the widths of the EPR lines attributed to the BEDT-TTF conducting sublattice correlate with the widths of the EPR lines associated with the magnetic sublattice of the Mn(dca) ₃ ^? counterion in the structure of salt II. This correlation suggests that the antiferromagnetic ordering in the magnetic sublattice of compound II affects the spin-lattice relaxation in the BEDT-TTF sublattice. The dependence of the magnetic moment on the magnetic field for compound II at a temperature of 2 K is typical of weakly frustrated uniaxial antiferromagnets and exhibits a kink in a magnetic field of 20 kOe, which corresponds to spin-flop transitions.     

Commensurate and incommensurate states of a spin density wave in a quasi-two-dimensional system with an anisotropic energy spectrum in an external magnetic field of arbitrary direction relative to magnetization

A theory of thermodynamic properties of a spin density wave (SDW) in a quasi-two-dimensional system (with a preset impurity concentration x) is constructed. We choose an anisotropic dispersion relation for the electron energy and assume that external magnetic field H has an arbitrary direction relative to magnetic moment M _Q . The system of equations defining order parameters M _Q ^z , M _Q ^σ , M _z , and M ^σ is constructed and transformed with allowance for the Umklapp processes. Special cases when H ‖ M _Q and H ⊥ M _Q (H _Z H ^σ = 0) are considered in detail as well as cases of weak fields H of arbitrary direction. The condition for the transition of the system to the commensurate and incommensurate states of the SDW is analyzed. The concentration dependence of magnetic transition temperature T _M is calculated, and the components of the order parameter for the incommensurate phase are determined. The phase diagram (T,~x) is constructed. The effect of the magnetic field on magnetic transition temperature T _M is analyzed for H _Z H ^σ = 0, and longitudinal magnetic susceptibility χ‖ is calculated; this quantity demonstrates the temperature dependence corresponding to a system with a gap for x < x _c and to a gapless state for x > x _c . In the immediate vicinity of the critical impurity concentration (x ～ x _c ), the temperature dependence of the magnetic susceptibility acquires a local maximum. The effect of anisotropy of the electron energy spectrum on the investigated physical quantities is also analyzed.     

Synthesis and EPR spectroscopy of nitroxyl derivatives of the C60 fullerene

The 2,2,5,5-tetramethyl-3-imidazoline-3-oxy-1-oxyl-4-(azidophenyl) derivatives of the C₆₀ fullerene with one (compound I), two (compound II), and three (compound III) nitroxyl groups are synthesized and studied by EPR spectroscopy. It is demonstrated that successive addition of nitroxyl radicals to C₆₀ leads to a decrease in the rotational mobility of molecules. Chromatographically inseparable isomers are found for compounds II and III.     

The nature of anharmonicity and anomalous piezoelectric properties of ferroelectric SbSBr crystal

The contribution of soft mode at Sb atom's sites, to the temperature dependences of Sb atom's equilibrium position's difference Δz(T) has been studied theoretically, when SbSBr crystal is deformed along a(x), b(y) and c(z)-axis in paraelectric phase and is deformed along c(z)-axis in ferroelectric phase. The largest change of Δz₃₃(T) occurs in the ferroelectric phase near the phase transition temperature in the range from 16 K to 21 K. The temperature dependence of Sb atom's equilibrium position's displacements Δz₃₃ is very similar to the temperature dependence of experimental piezoelectric modulus, when SbSBr crystal is deformed in the direction of c(z)-axis in ferroelectric phase.     

Twinning and short-range order in ordered titanium monoxide

Electron diffraction was used to study the annealed titanium monoxide TiO_1.087 containing the monoclinic ordered phase Ti₅O₅. The diffraction pattern of titanium monoxide in the (112)* _B1 plane of the reciprocal lattice of the parent B1 cubic structure contains not only structural, superstructural, and additional reflections but also a system of planar diffuse strips. It has been established that part of the additional reflections are twins of the superstructure reflections of the monoclinic ordered phase; the twinning plane is the ( $\overline 1 \overline 1 1$ ) plane of the reciprocal lattice of the parent cubic phase. The diffuse scattering contours cover finite plane areas in the reciprocal space characterized by the wave vectors K ₁₀₀ ～ ± (h + 0.07)k ₁₀₀, K ₀₁₀ ～ ±(k + 0.07)k ₀₁₀, and K ₀₀₁ ～ ±(l + 0.07)k ₀₀₁ in the B1 structure. The diffuse scattering is caused by short-range displacement order. Short-range substitution order and the corresponding diffuse scattering are absent.     

Theoretical studies of ground and excited states in a series of Zn(II) complexes,derived from thiourea and thiosemicarbazide

Theoretical studies for a series of mono- and binuclear zinc (II) complexes Zn(CH₃COO)₂(H₂L)₂ [H₂L = N-2-propenyl-N ^′-2-pyridinylthiourea] (A), Zn₂(CH₃COO)₂(H₃L-a)₂ [H₃L-a = 2-[(2-hydroxy phenyl)methylene]hydrazine-N-phenylcarbothioamide] (B), and Zn(H₃L-b)₂ [H₃L-b = 2-[(2-hydroxy phenyl)methylene]hydrazine-N-(2-propenyl)carbothioamide] (C) have been performed on their structures and excited-state absorption spectra. The singlet ground-state geometries are fully optimised at three DFT levels, i.e., B3LYP, B3PW91, and M06. Different geometries, i.e., strongly distorted tetrahedral coordination environment in complex A, distorted square-pyramidal environment in complex B, and irregular octahedral mode in complex C are identified. Consequently, the spectroscopic properties are calculated by means of time-dependent density functional theory (TDDFT) with the Polarisable Continuum Model (PCM) based on the optimised gas-phase geometries. Three absorption peaks are identified for every complex, which are in good agreement with the experimental ones. For complex A, all three absorption peaks centered at 280.33 nm, 268.09 nm, and 250.87 nm, respectively, are ascribed to the (p,π) → π* transition with a mixed intraligand charge-transfer (ILCT)/ligand-ligand charge-transfer (LLCT) character. The composition of frontier orbitals involved in major absorption bands for the three complexes shows similarities, which results in the almost homologous transition attributions and characteristics. A remarkable bathochromic shift in the lowest-lying absorption band is observed for complexes B and C as compared with complex A, which is attributed to the decreased H (HOMO)-L (LUMO) energy gap (ΔE |HOMO-LUMO|) by the formation of conjugate metallocycles in complexes B and C.     

Diffraction of electrons in the CubicTi5O5 superstructure of titanium monoxide

Annealed titanium monoxide TiO_1.087 has been studied by the electron diffraction method. A cubic model of the Ti₅O₅ superstructure (Ti₅O₅ (Ti₉₀?₁₈O₉₀??₁₈)) of nonstoichiometric titanium monoxide Ti _x O _z has been proposed on the basis of experimental data and representations about the disorder-order transition channel. It has been shown that reflections observed on the electron diffraction pattern are identified in the space group $Pm\bar 3m$ . The period of the unit cell of the cubic Ti₅O₅ superstructure is larger than that for the B1 basic disordered structure of Ti _x O _z monoxide by a factor of 3. The disorder-order transition channel Ti _x O _z (space group $Fm\bar 3m$ )-Ti₅O₅ (space group $Pm\bar 3m$ ) includes 75 superstructure vectors of seven stars {k ₁₀}, {k ₇}, {k ₆₍₁₎}, {k ₆₍₂₎}, {k ₄₍₁₎}, {k ₄₍₂₎}, and {k ₁}. The distribution functions of Ti and O atoms over the sites of the cubic Ti₅O₅ (space group $Pm\bar 3m$ ) superstructure have been calculated.     

The Structure and EPR Behavior of Short Nitroxide Biradicals Containing Sulfur Atom in the Bridge

Two short nitroxide biradicals of similar composition: S(OR₆)₂ (1) and O=S(OR₆)₂ (2), where OR₆ is 1-oxyl-2,2,6,6-tetramethyl-4-oxypiperidine, have been studied by electron paramagnetic resonance spectroscopy, and X-ray structural analysis. Variations of the intramolecular electron spin exchange in the biradicals, dissolved in toluene and ethanol, as a function of temperature were characterized by changes in the isotropic ¹⁴N hyperfine splitting constant a, values of the exchange integral $ \left| J \right|, $ and compared with the X-ray structural data. Thermodynamic parameters of the conformational rearrangements were calculated. Geometry optimization and spin density distribution calculations of biradicals 1 and 2 were carried out on the DFT/UB3LYP/cc-pVdz and DFT/ROPBE/N07D levels of theory. Structural rigidity and probable differences in biradicals behavior are discussed.     

The Reaction of Synechocystis Catalase–Peroxidase (KatG) with Isoniazid Investigated by Multifrequency (9–285 GHz) EPR Spectroscopy

Three distinct electron paramagnetic resonance (EPR) spectra of radical intermediates formed as reactive intermediates in the catalytic cycle of Synechocystis catalase–peroxidase were identified. Multifrequency EPR spectroscopy, combined with site-directed mutagenesis and selective deuterium labeling of Trp and Tyr residues, allowed us to unequivocally assign such intermediates to an [Fe(IV) = O Por ^·+] species, the first committed intermediate in monofunctional peroxidases and two protein-based radicals, identified as Trp106 ^· and a Tyr ^· , formed subsequently to the [Fe(IV) = O Por ^·+] species by intramolecular electron transfer. Our recent characterization of the Mycobacterium tuberculosis catalase–peroxidase showed that the Trp ^· sites differ among these enzymes, and that the [Fe(IV) = O Trp ^· ] species was the reactive intermediate with the prodrug isoniazid. Accordingly, the question to address was whether the dissimilarity in the sites for the formation of the Trp ^· intermediates and in the geometry of the distal side was reflected by differences in the peroxidase-like reaction of Synechocystis and Mycobacterium tuberculosis catalase–peroxidases with the prodrug isoniazid. Our findings show that in the Synechocystis enzyme, the isoniazid substrate can get closer to the heme distal side and can react readily with the [Fe(IV) = O Por ^·+] species, at variance to the situation in the M. tuberculosis catalase–peroxidase. These results indicate that, as in the case of monofunctional peroxidases, the difference in the sites for the formation of the Trp ^· as alternative reactive intermediates to the [Fe(IV) = O Por ^·+] species is correlated to differences in substrate binding sites.     

EPR study of the ferroelectric phase transition in chromium-doped DMAAS

X-band electron paramagnetic resonance (EPR) investigations of single crystals of Cr³⁺-doped dimethylammonium aluminium sulphate hexahydrate are presented from 100 K to room temperature. The crystal undergoes a phase transition at 152 K from the ferroelastic to the ferroelectric phase. The spin-Hamiltonian parameters have been determined for both phases. The spin-Hamiltonian parameters in the ferroelectric phase are:g=1.980±0.003,b ₂ ⁰ =(1140±15)·10^?4 cm^?1,b ₂ ² =(214±10)·10^?4 cm^?1. Remarkable EPR line width changes confirm the order-disorder character of the ferroelectric phase transition on a microscopic level and demonstrate that the dimethylammonium reorientation freezing-out is the prime reason for this transition.