Thermal and EPR spectroscopic studies of novel coordination compound trans-bis(acesulfamato)tetraaquazinc(II) with Mn(II) impurity

The thermogravimetric analysis (TGA) and electron paramagnetic resonance (EPR) studies of powder and single crystals of bis(acesulfamato)tetraaquazinc(II), Zn(acs)(2)(H(2)O)(4), a novel coordination compound, are carried out. Previously synthesized bis(acesulfamato) tetraaquamanganese(II), Mn(acs)(2)(H(2)O)(4), is included into the host in trace amount as a paramagnetic probe for EPR analysis. Single crystal EPR spectra at room temperature are resolved and discussed. Low temperature EPR spectra down to 90K do not show remarkable change. At higher temperatures, however, the TGA and EPR spectra show changes around 335 K and 395 K; the causes and the mechanisms of changes are discussed.     

Single crystal EPR and optical studies of paramagnetic ions doped zinc potassium phosphate hexahydrate—Part I: Cu(II)—a case of orthorhombic symmetry

Single crystal electron paramagnetic resonance (EPR) studies on Cu(II) doped zinc potassium phosphate hexahydrate (ZPPH) were carried out at room temperature. The angular variation spectra in the three orthogonal planes indicate that the paramagnetic impurity has entered the lattice substitutionally in place of Zn(II) and the spin Hamiltonian parameters calculated from these spectra are g(xx) = 2.188, g(yy) = 2.032, g(zz) = 2.373, Axx = 50 G, Ayy = 65.0 G and Azz = 80 G. The g and A tensors were coincident and these values matched fairly well with the values obtained from powder spectrum. The bonding parameters have also been calculated.     

Thermal and optical properties of Cu(II)-doped magnesium rubidium sulfate hexahydrate crystals

Single crystals of pure and cupric ion (Cu(II))-doped magnesium rubidium sulfate hexahydrate (MRSH) were prepared by slow evaporation of saturated solution technique (SEST) and the influence of dopant Cu(II) on the MRSH crystals has been investigated. Incorporation of Cu(II) into the crystalline matrix was confirmed by energy dispersive spectroscopy (EDS) and electron paramagnetic resonance (EPR) spectroscopy. Thermogravimetric (TG) analysis of the doped sample reveals the faster rate of degradation. EPR spectrum of the MRSH both at room temperature and at 77 K indicates the presence of Cu(II) in the interstitial position. The grown crystals were also characterized by UV–VIS and IR spectroscopy. The surface morphology of the doped sample studied by scanning electron microscopy (SEM) indicates different morphology at various magnifications. The non-linear optical (NLO) property measured using second harmonic generation (SHG) efficiency test reveals that the non-linearity is not facilitated by doping of Cu(II).     

Electron paramagnetic resonance studies of Cu2+ ion in tetraaqua-di(nicotinamide)Ni(II)-saccharinates single crystals

X-band (approximately 9.8 GHz) electron paramagnetic resonance (EPR) measurement at ambient temperature in three mutually perpendicular planes have been carried out on a single crystal of Cu2+ doped mixed ligand complex of Ni(II) with saccharin and nicotinamide [Ni(Nic)2(H2O)4](sac)2. The angular dependent spectra showed that the Cu2+ ion enters Ni2+ sites in the lattice and distorted local environment of Ni2+ site. The principal g and A values, covalency parameter (alpha'2), mixing coefficients (alpha and beta) and Fermi contact term (K) have been evaluated from the EPR analysis. The ground-state wave function of the Cu2+ ion has been constructed using the alpha'2, alpha and beta values. The nature of the distortion present in the lattice is obtained from the values of the mixing coefficients.     

Vibronic effects in Cu(II)-doped Ba2Zn(HCO2)6 x 4 H2O

The temperature-dependent electron paramagnetic resonance (EPR) spectrum of approximately 1% Cu(II) ions doped into Ba 2Zn(HCO2)6 x 4 H2O was analyzed at the Q-band frequencies over the temperature range 100-350 K to obtain structural information about the local environment. It can be concluded that the host crystal imparts a large orthorhombic strain which mainly corresponds to a tetragonal compression imposed onto the Cu(II)O6 species. This results in a copper center which adopts an orthorhombically distorted elongated geometry with the elongated axis perpendicular to the direction of the tetragonal compression due to the host crystal. There are two possible axes of elongation, and these represent two conformers separated by approximately 320 cm(-1). The thermal population of the higher energy level averages the g values, giving the observed temperature-dependent EPR spectra. The averaging process is between vibronic levels that are localized at two different minima of a single ground-state potential energy surface. These vibronic levels correspond to vibrational levels having different electronic properties. The determination of the host lattice strain parameters from the Cu(II) EPR spectra means that the guest ion is used as a probe of the environment of the Zn(II) site. The structural data derived from the lattice strain parameters are correlated with those from the Ba 2Zn(HCO2)6 x 4 H2O crystal structure.     

Transition metal polymeric chelates: Spectral, magnetic, thermal behaviour of polymeric chelates of poly(resacetophenone diyl ethylene)s with Ni(II), Cu(II), Mn(II), Zn(II) and Co(II)

Polymeric chelates of the type [ML₂]_n where M = Ni(II), Cu(II), Zn(II) or Co(II), L = poly(resacetophenone diyl ethylene)s, andn= degree of polymerization, have been synthesized. Their structures have been elucidated on the basis of analytical, magnetic, electronic and IR spectral studies. Electronic spectra in conjunction with magnetic moments are in accord with an octahedral environment around the central metal ion in all polymeric chelates except Cu(II) and Zn(II) polymeric chelates which have been shown to possess square planar and tetrahedral geometries, respectively. IR spectral studies further suggest that the metal ions are coordinated through the oxygens of the carbonyl and the phenolic hydroxyl groups. All the chelates are paramagnetic except Zn(II), which is found to be diamagnetic.     

Single crystal EPR of Cu(II) doped Cd(C5H5NO)6(BF4)2--an example of reduced metal hyperfine coupling constant

Electron paramagnetic resonance (EPR) studies have been carried out on Cu(II) doped Cd(C5H5NO)6(BF4)2 in single crystal and powder forms at 300 K. Angular variation of hyperfine structure lines shows the presence of two magnetic sites, indicating possible twinning in the Cd lattice. From the mean values of two sites, the angular variation plot is fitted to an orthorhombic spin Hamiltonian. The observed orthorhombic g values and the very low A11 value ([A11] = 107.8 x 10(-4) cm(-1)) are unusual for a hexakis coordinated system. This unique behavior is explicable in terms of the static Jahn-Teller (JT) effect.     

Crystal structure and EPR studies of mixed ligand complex of cobalt(II) with saccharin and ethylisonicotine

The tetraaquabis(ethylisonicotinate)cobalt(II) disaccharinate, [Co(ein)2(H2O)4].(sac)2, (CENS), (ein: ethylisonicotinate and sac: saccharinate) complex has been synthesized and its crystal structure has been determined by X-ray diffraction analysis. The title complex crystallizes in monoclinic system with space group P2(1)/c and Z=2. The Co(II) cations present a slightly distorted CoN2O4 octahedral environment, with equatorially coordinated water molecules and axially pyridine N-bound ethylisonicotinate ligands. The magnetic environments of Cu2+-doped Co(II) complex have been identified by electron paramagnetic resonance (EPR) technique. Cu2+-doped CENS single crystals have been studied at room temperature in three mutually perpendicular planes. The calculated results of the Cu2+-doped CENS indicate that Cu2+ ion substitute with the Co2+ ion in the host lattice. The angular variations of the EPR spectra have shown that two different Cu2+ complexes are located in different chemical environments, and each environment contains two magnetically inequivalent Cu2+sites in distinct orientations occupying substitutional positions in the lattice and show very high angular dependence. The cyclic voltammogram of the title complex investigated in dimethylformamide (DMF) solution exhibits only metal centered electroactivity in the potential range -1.0-1.25V versus Ag/AgCl reference electrode.     

An EPR study of various compounds of copper (II) and silver (II)

The electron paramagnetic resonance (EPR) spectra in the three-centimeter and decimeter wavelength ranges have been studied in liquid and frozen solutions of copper(II) and silver(II) in ortho-, pyro-, and metaphosphoric acids, sulfuric acid, and nitric acid, and also in liquid and frozen solutions of Cu(II) in fluorosilicic acid. The parameters of the spin Hamiltonian have been determined. It has been shown that the magnetic ion M(II) in these compounds is situated in an axially distorted octahedron, formed by six oxygen atoms. The EPR spectra of frozen solutions of M(II) in ortho-, pyro-, and metaphosphoric acids, obtained by the procedure described in the present paper, do not differ from one another. Study of the EPR spectra over a wide range of frequencies has shown that for the Cu(II) compounds the condition of strong fields is satisfied as far as 800–1000 MHz, but on going to lower frequencies the condition of intermediate fields is satisfied. For the Ag(II) compounds the condition of strong fields is satisfied throughout the entire range of frequencies studied. It can be seen from the experimental results obtained that the values of the anisotropic hyperfine splitting (HFS) constants, reduced to unit magnetic moment of the corresponding nuclei, increase on going from the Cu(II) ions with n=3 to the Ag(II) ions with larger principal quantum number (n=4).In conclusion the authors thank B. M. Kozyrev for extensive discussion of the results and L. F. Shatrukov for assistance with the calculation of the spectra on the electronic computer.     

EPR and optical absorption studies of VO(II)-doped zinc Tris thiourea sulfate.

Electron paramagnetic resonance (EPR) of vanadyl ion as an impurity in polycrystalline zinc tris thiourea sulfate (ZTS), a prominent nonlinear optical host, has been studied at X-band frequencies at room temperature. Spin-Hamiltonian parameters and molecular orbital coefficients have been calculated. The optical absorption spectra have also been studied to deduce the crystal field parameters.     

EPR study of Cu(2+)-doped tetraaqua-di(nicotinamide)Co(II) saccharinate single crystals

The electron paramagnetic resonance spectra of Cu(2+) impurities in [Co(nicotinamide)(2)(H(2)O)(4)](saccharinate)(2) single crystals have been studied at ambient temperature in three mutually perpendicular planes. The angular variation of the spectra shows that the Cu(2+) ion substitutes the Co(2+) site in the lattice. The EPR spectra of Cu(2+) ions are characteristic of tetragonally elongated octahedral site. The spin-Hamiltonien parameters were obtained from the single crystal EPR analysis. The ground-state wave function of Cu(2+) ion in the lattice has been constructed.     

EPR studies of Cu2+ in tetraaqua-di(nicotinamide) Zn(II)-saccharinate single crystals

Electron paramagnetic resonance (EPR) studies of copper ions, Cu(II), as paramagnetic impurity in tetraaqua-di(nicotinamide) Zn(II)-saccharinates single crystals [Zn(nic)2(H2O)4](sac)2, have been investigated at ambient temperature. The detailed EPR analysis shows the only one site and the copper ion entered the lattice substitutionally in place of Zn(II). The spin-Hamiltonian parameters were obtained from the single crystal EPR analysis. By using the EPR data, molecular bonding coefficient and the Fermi contact interaction terms have been evaluated. Superhyperfine splittings were observed.     

Molecular magnetic properties of two-copper(II) containing complexes [Cu(II) (1-phenylamidino-O-n-butylurea) en (H2O)]2(2+) and [Cu(II) sulphato-mono (1-phenylamidino-O-methylurea)]2. An EPR study

Electron paramagnetic resonance (EPR) investigations were conducted on [Cu(II) (1-phenylamidino-O-n-butylurea) en (H2O)]2(2+) (1) and [Cu(II) sulphato-mono (1-phenylamidino-O-methylurea)]2 (2) respectively, in the temperature range 300-77K. Fine structure characteristics of S = 1 system, was observed in both complexes with zero field splitting of 0.0525 and 0.0225 cm(-1), respectively, suggesting the formation of dimeric complexes. The presence of the half-field signal (DeltaMs= +/-2), in the complex 1, further confirmed the formation of dimer. The temperature dependence of EPR signal intensity has given evidence for the ferromagnetic (FM) coupling between the two Cu2+ ions. The isotropic exchange interaction constants J, were evaluated from this and were found out to be approximately 57 and approximately 27 cm(-1), respectively, for the complexes 1 and 2. The photoacoustic spectra of these complexes had shown a band around 26,400 cm(-1) characteristic of metal-metal bonding giving an independent support for the existence of dimeric Cu2+ species. The high magnetic moment values at room temperature for complex 1 (2.68 microB) and complex 2 (2.00 microB), obtained from the magnetic susceptibility measurements, support the formation of ferromagnetically coupled Cu2+ dimers.     

EPR and electronic spectral properties of aryl-substituted bis(dithiophosphato)copper(II) complexes

The spectral properties of bis(diaryl-dithiophosphato)copper(II) complexes, [Cu(S(2)P(OR)(2))(2)], with R = o-cresyl (complex I) and 2,6-dimethylphenyl (complex II) are studied by EPR- and vis spectroscopy. In solid (powder) state both complexes exhibit dark brown colour and are paramagnetic. Room temperature EPR spectra of the complexes dissolved in non-coordinating (C(6)H(5)CH(3), C(5)H(12), C(6)H(14)), acceptor (CHCl(3), CCl(4)) or donor (DMFA, DMSO) solvents have typical features of the chromophore CuS(4). In non-coordinating and acceptor solvents their isotropic EPR parameters are: g(iso)=2.047+/-0.003, (Cu)A(iso) = 7.2+/-0.1 mT and (P)A = 0.95+/-0.1 mT. An absorption band characterizes the vis spectra in these solvents with a maximum at 427 nm, due to a ligand-to-metal charge-transfer transition. One hour after dissolution the absorbance at 427 nm follows Beer's law with molar absorptivity (epsilon) about 11000, which does not change significantly after 24 h staying at room temperature or after 30 min heating at 50 degrees C. Both DMFA and DMSO exhibit specific solute-solvent interaction with the acceptor centre of copper complex yielding an axial adduct, with increased g-factor and decreased (hf)A compared to the initial complex. An additional EPR signal with unresolved hyperfine structure is also detected in DMSO. EPR and vis intensities of both bis(diaryl-dtp)Cu(II) complexes decrease after dissolution in both solvents. Moreover, they are EPR silent in pyridine and do not show any absorption in the vis spectra.     

Single crystal EPR and optical studies of paramagnetic ions doped zinc potassium phosphate hexahydrate--part II: VO(II)--a case of substitutional site.

Single crystal electron paramagnetic resonance (EPR) studies were carried at room temperature for VO(II) doped zinc potassium phosphate hexahydrate. The results indicate that the paramagnetic impurity has entered the lattice only substitutionally, as confirmed by the single crystal rotations. The spin Hamiltonian parameters calculated from the spectra are g parallel = 1.9356, g perpendicular = 1.9764, A parallel = 200.9 G and A perpendicular = 76.5 G. The optical absorption spectrum exhibits three bands (800, 670 and 340 nm) suggesting the C4v symmetry and the optical parameters evaluated are Dq = 1492, Ds = -3854 and Dt = 186 cm(-1).     

Spectral studies on VO ions in potassium thiourea bromide single crystals using EPR and optical absorption spectroscopy

Electron paramagnetic resonance (EPR) studies have been carried out on VO²⁺ ions doped in single crystals of ferroelectric material, potassium thiourea bromide (PTB) at room temperature and in the temperature range 103–343 K on X-band MW frequency. An isotropic octet spectrum characteristic of VO²⁺ ion was obtained due to the fast re-orientation of the VO²⁺ in PTB lattice, which exhibits glassy nature at certain range around room temperature. The temperature dependant EPR spectra of VO²⁺ ions in this host lattice has been attributed to the occurrence of multiple phase transitions due to the combined environment effects of KBr and thiourea materials in the single crystal. From the optical absorption spectrum, the crystal field splitting parameter Dq, tetragonal parameters Ds and Dt have been evaluated and discussed.     

Synthesis and spectroscopic studies on copper(II) binuclear complexes of 1-phenylamidino-O-alkylurea (alkyl = n-propyl, n- and iso-butyl) with 1,3-diaminopropane or ethylenediamine

Copper(II) binuclear complexes [Cu(II)(1-phenylamidino-O-n-propylurea)tn]2 (H2O)2(Cl2)2 (1), [Cu(II)(1-phenylamidino-O-n-butylurea)tn]2(H2O)2(Cl2)2(2), [Cu(II)(1-phenylamidino-O-i-butylurea)tn]2(H2O)2(Cl2)2(3), and [Cu(II)(1-phenyamidino-O-i-butylurea)en]2(H2O)2(Cl2)2 (4) have been reported. The binuclear complexes 3 and 4 crystallize in a monoclinic structure with unit cell dimensions a = 15.252(17) A, b = 14.682(10) A, c = 13.606(13) A, and beta = 111.2(1) degrees and a = 15.278(35) A, b = 14.665(21) A, c = 13.603(27) A, and beta = 111.1(1) degrees , respectively. The EPR spectra of all the solid complexes at room temperature consisted of fine-structure transitions (DeltaM(s) = 1) with zero-field splitting (ZFS) of 0.0500 cm(-1) and a half-field signal (DeltaM(s) = 2) at ca. 1600 G, suggesting the formation of binuclear complexes (S = 1). From the observed ZFS, we estimated the average Cu-Cu distance. From the temperature dependence of the EPR signal intensity, we evaluated the isotropic exchange interaction constant J. It appears that the exchange interaction between the two interacting spins of the binuclear complexes is ferromagnetic in nature. The formation of ferromagnetically coupled copper binuclear complexes was further confirmed from the high magnetic-moment values at room temperature. When the EPR spectra were recorded in the temperature range 300-400 K, it was observed that the triplet-state EPR signal completely and irreversibly disappeared at ca. 380 K with the appearance of a new signal attributable to the mononuclear complex (S = 1/2). Thermal studies of these complexes in this temperature range suggested the loss of two water molecules, which might be responsible for binding two mononuclear species. EPR, IR, and thermal studies indicate a long-range ferromagnetic exchange mediated through hydrogen bonding between copper(II) ions (S = 1/2).     

EPR studies of VO2+ ions in kainite single crystals

Electron paramagnetic resonance (EPR) spectra of VO2+ ions doped in Kainite (a mineral salt) single crystals and powder were recorded at room temperature at X-band frequencies.The angular variation studies of the spectra indicate that the VO2+ ion enters Mg2+ ion site substitutionally. The principal values of g and A-tensors were determined from the EPR spectral studies. Using these EPR parameters, the molecular orbital bonding parameters of VO2+ ion in the lattice have been evaluated and discussed.     

Electron paramagnetic resonance study on manganese doped tetrathioureacopper(I) chloride single crystal

Electron paramagnetic resonance (EPR) spectrum of a NLO material, manganese doped tetrathioureacopper(I) chloride single crystal was investigated at room temperature. The spectra reveal that manganese exists in tetravalent state in the host lattice in interstitial position and the crystal becomes NLO material whereas the pure crystal does not show NLO property. The spin Hamiltonian parameters are evaluated as g=1.9872 and A=157G. The transmission spectrum and the second harmonic generation efficiency confirm that the manganese doped single crystal exhibit NLO property.     

Ferromagnetic Mn(II).Cu(II) Exchange in the New Bimetallic Quasi-2-D Compound Cu(op)(2)MnCl(4) (op = 1,4-Diazacycloheptane)

The synthesis, crystal structure, and magnetic properties are reported for the new bimetallic compound Cu(op)(2)MnCl(4), where op = HN(CH(2))(5)NH. The compound, C(10)H(24)N(4)Cl(4)CuMn, crystallizes in the monoclinic space group P2(1)/n. Cell dimensions are as follows: a = 15.316(3) ?, b = 16.608(3) ?, c = 7.141(2) ?, beta = 100.01(5) degrees, Z = 4. The structure consists of well-separated and magnetically equivalent layers which are composed of chloride-bridged Cu(op)(2)MnCl(4) binuclear units connected by rather loose Cu-N-H.Cl-Mn contacts. The MnCl(4) fragment approximates tetrahedral symmetry. The Cu(II) geometry is (4 + 1) square-pyramidal with the apical position occupied by a bridging chloride ligand and the basal ones by the nitrogen atoms from the organic ligands. The shortest interlayer M.M separations, approximately 7 ?, are of the Mn.Cu type. Magnetic susceptibility and single-crystal EPR measurements for the compound have been carried out over the range 4-300 K. At room temperature the chiT product (per MnCu unit) has a value of 4.84 emu.mol(-)(1).K, close to that expected for uncoupled S = (5)/(2) and S = (1)/(2) spins. When the temperature is lowered, chiT remains almost constant until 80-90 K, slightly increases to reach a maximum at approximately 13 K (5.21 emu.mol(-)(1).K), and then rapidly decreases. Comparison between theory and experiment, made with use of both a mean field corrected dimer model and an approximate 2-D model, indicates that Mn(II).Cu(II) exchange is ferromagnetic within the dimers (J(1) approximately 2.6 cm(-)(1)) and antiferromagnetic among dimers, with J values between -0.07 and -0.03 cm(-)(1) (the interaction Hamiltonian is of the form H = -2JS(A).S(B)). Single-crystal EPR spectra recorded along the a, b, and c axes show a large temperature dependence of the g factors: at 4.2 K, g(a) = 2.10, g(b) = 1.96, and g(c) = 2.01. This pattern substantiates the presence of a 2-D magnetic structure with ferromagnetic intradimer exchange and interdimer antiferromagnetic exchange of weaker magnitude. The opposite signs of the interactions are ascribed to the local symmetries of the Cu(II) and Mn(II) ions.