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Single crystal EPR studies of Mn(II)-doped zinc ammonium phosphate hexahydrate (ZnNH4PC4·6H2O) have been reinvestigated at room temperature. Single crystal rotations along the three orthogonal axes indicate that the
spin Hamiltonian parameters for the interstitial site are:g
xx
= 1.966,g
yy
= 1.972,g
zz
= 1.976;D
xx
= -12.28 mT,D
yy
= -2.09 mT andD
zz
= 14.37 mT;A
xx
= 9.06 mT,A
yy
= 9.06 mT andA
zz
= 11.09 mT;a = -0.11 mT. These parameters differ considerably from the previous report of Chand and Agarwal and indicate the orthorhombic
nature of the paramagnetic impurity. The impurity is found to enter the lattice interstitially, in contrast to earlier prediction
of substitutional position. The percentage covalency of the Mn-0 bond has been estimated. 相似文献
2.
Vidjayacoumar B Ilango S Ray MJ Chu T Kolpin KB Andreychuk NR Cruz CA Emslie DJ Jenkins HA Britten JF 《Dalton transactions (Cambridge, England : 2003)》2012,41(26):8175-8189
A rigid NSN-donor proligand, 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylthioxanthene (H(2)[TXA(2)], 1) was prepared by palladium-catalyzed coupling of 2,6-diisopropylaniline with 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylthioxanthene. Deprotonation of 1 using (n)BuLi provided Li(2)(DME)(2)[TXA(2)] (2), and subsequent reaction with UCl(4) afforded [Li(DME)(3)][(TXA(2))UCl(3)] (4). The analogous NON-donor ligated complex [(XA(2))UCl(3)K(DME)(3)] [3; XA(2) = 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylxanthene] was prepared by the reaction of K(2)(DME)(x)[XA(2)] with UCl(4). A cyclic voltammogram (CV) of 3 in THF/[NBu(4)][B(C(6)F(5))(4)] at 200 mV s(-1) showed an irreversible reduction to uranium(III) at E(pc) = -2.46 V versus FeCp(2)(0/+1), followed by a product wave at E(1/2) = -1.83 V. Complex 4 also underwent irreversible reduction to uranium(iii) [E(pc) = -2.56 V], resulting in an irreversible product peak at E(pa) = -1.83 V. One-electron reduction of complexes 3 and 4 using K(naphthalenide) under an argon atmosphere in DME yielded 6-coordinate [(XA(2))UCl(DME)] (5) and the thermally unstable 7-coordinate [(TXA(2))U(DME)Cl(2)Li(DME)(2)] (6), respectively. The U-S distances in 4 and 6 are uncommonly short, the C-S-U angles are unusually acute, and the thioxanthene backbone of the TXA(2) ligand is significantly bent. By contrast, the xanthene backbone in XA(2) complexes 3 and 5 is planar. However, κ(3)-coordination and an approximately meridional arrangement of the ancillary ligand donor atoms is maintained in all complexes. DFT and Atoms in Molecules (AIM) calculations were carried out on 3, 4, 5, 6, [(XA(2))UCl(3)](-) (3B), [(TXA(2))UCl(2)(DME)](-) (6B) and [(TXA(2))UCl(DME)] (6C) to probe the extent of covalency in U-SAr(2) bonding relative to U-OAr(2) bonding. 相似文献
3.
Anandalakshmi H Sougandi I Velavan K Venkatesan R Rao PS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(11):2661-2666
Single crystal electron paramagnetic resonance (EPR) studies of Mn(II) doped zinc potassium phosphate hexahydrate have been carried out at room temperature. Single crystal rotations along the three orthogonal axes indicate orthorhombic symmetry with spin-Hamiltonian parameters as: g(xx) = 1.9997; g(yy) = 1.9538; g(zz) = 1.9524, D(xx) = 15.49 mT; D(yy) = 0.22 mT; D(zz) = -15.71 mT, A(xx) = 11.70 mT; A(yy) = 10.53 mT; A(zz) = 10.42 mT and a = 0.8 x 10(-4) cm(-1). A large E term indicates considerable distortion from axial symmetry. The impurity is found to enter the lattice substitutionally. The distortion axis for the impurity has been identified along one of the Zn-O bond directions in the crystal. 相似文献
4.
R. Srinivasan I. Sougandi R. Venkatesan P. Sambasiva Rao 《Journal of Chemical Sciences》2003,115(2):91-102
A bimetallic nickel(II) complex with the ligand Hsalamp (2-[(4-methyl-pyridin-2-ylimino)-methyl]-phenol), having the molecular
formula, Ni2C26H22 N4O10Cl2, is synthesized and characterized by elemental, UV-Vis, IR and EPR studies. The IR spectrum confirms the presence of coordinated
perchlorate ion and the UV-Vis. spectrum substantiates that the geometry around the metal ion is distorted square pyramidal.
In the solvent methanol, the complex undergoes dissociation indicating the nature of the complex to be 1:2 electrolyte. The
single crystal EPR studies indicate that the zero-field splitting is not large and the spectra can be observed even at room
temperature, not so common for a nickel(II) ion. The spin Hamiltonian parameters calculated from single crystal rotations
are:g - 2.377, 2.219, 2.071 and D - 9.7, 4.2 and -13.9 mT. Optical and electron paramagnetic spectral data have been used to obtain
the parametersDq,B andC. 相似文献
5.
I. Sougandi T. M. Rajendiran R. Venkatesan P. Sambasiva Rao 《Journal of Chemical Sciences》2002,114(5):473-479
Single crystal EPR studies of VO(II)-doped cadmium potassium phosphate hexahydrate (CPPH) have been carried out at room temperature.
The angular variation spectra in the three orthogonal planes indicate that the paramagnetic impurity has entered the lattice
only substitutionally in place of Cd(II). Spin Hamiltonian parameters have been obtained from single crystal data. Powder
spectra show a set of eight parallel and perpendicular features indicating the presence of only one site. The admixture coefficients
have been calculated from the data, which agree well with the literature values. 相似文献
6.
Sougandi I Venkatesan R Rao PS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(11):2653-2660
Single crystal electron paramagnetic resonance (EPR) studies of Cu(II) doped cobalt ammonium phosphate hexahydrate have been carried out from 300 to 77 K, with single crystal rotation in all the three planes at 153 K, since the spectra are well resolved at this temperature. The angular variation studies indicate only one site in substitutional position with spin-Hamiltonian parameters as g: 2.404, 2.155, 2.063 and A: 11.58, 3.49, 2.07 mT. The reduction in one of the principal A value has been explained by considering considerable admixture of d(x(2)-y(2)) ground state with d(zeta(2)) excited state. The admixture coefficients of ground state wave function are: a = 0.2500; b = 0.9663; c = 0.0520; d = 0.0210; e = -0.0210, where a and b correspond to admixture coefficients for d(zeta(2)) and d(x(2)-y(2)) , respectively. Parameters kappa = 0.5140; P = 113 X 10(-4) cm(-1); alpha(2) = 0.7897; alpha = 0.8887; and alpha' = 0.5262 have also been calculated, indicating considerable covalency. The powder spectrum at room temperature is unresolved, whereas it is better resolved at 77 K, with spin-Hamiltonian parameters matching well with the single crystal values of 153 K. Powder spectrum at 77 K has been simulated, which agrees with the experimental one. The spin-lattice relation times are measured from the line width of the resonance lines recorded at different temperature. 相似文献
7.
Sougandi Ilango Mahalakshmi Rajaram Kannappan Ramu Rajendiran Thekkelnayackanpatti M. Venkatesan Rangarajan Sambasiva Rao Pillutla 《Transition Metal Chemistry》2002,27(5):512-519
The synthesis, reduction, optical and e.p.r. spectral properties of a series of new binuclear copper(II) complexes, containing bridging moieties (OH–, MeCO2
–, NO2
–, and N3
–), with new proline-based binuclear pentadentate Mannich base ligands is described. The ligands are: 2,6-bis[(prolin-1-yl)methyl]4-bromophenol [H3L1], 2,6-bis[(prolin-1-yl)methyl]4-t-butylphenol [H3L2] and 2,6-bis[(prolin-1-yl)methyl]4-methoxyphenol [H3L3]. The exogenous bridging complexes thus prepared were hydroxo: [Cu2L1(OH)(H2O)2] · H2O (1a), [Cu2L2(OH)(H2O)2] · H2O (1b), [Cu2L3(OH)(H2O)2] · H2O (1c), acetato [Cu2L1(OAc)] · H2O (2a), [Cu2L2(OAc)] · H2O (2b), [Cu2L3(OAc)] · H2O (2c), nitrito [Cu2L1(NO2)(H2O)2] · H2O (3a), [Cu2L2(NO2)(H2O)2] · H2O (3b), [Cu2L3(NO2)(H2O)2] · H2O (3c) and azido [Cu2L1(N3)(H2O)2] · H2O (4a), [Cu2L2(N3)(H2O)2] · H2O (4b) and [Cu2L3(N3)(H2O)2] · H2O (4c). The complexes were characterized by elemental analysis and by spectroscopy. They exhibit resolved copper hyperfine e.p.r. spectra at room temperature, indicating the presence of weak antiferromagnetic coupling between the copper atoms. The strength of the antiferromagnetic coupling lies in the order: NO2 N3 OH OAc. Cyclic voltammetry revealed the presence of two redox couples CuIICuII CuIICuI CuICuI. The conproportionality constant K
con for the mixed valent CuIICuI species for all the complexes have been determined electrochemically. 相似文献
8.
Deepa S Velavan K Sougandi I Venkatesan R Sambasiva Rao P 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(11-12):2482-2487
Single crystal EPR study of VO(II)-doped magnesium potassium phosphate hexahydrate has been carried out at room temperature. Single crystal rotations in the three orthogonal planes indicate that the paramagnetic impurity has entered the lattice in place of magnesium ions by replacing the equatorial and axial coordinated water molecules. The spin Hamiltonian parameters obtained for the two substitutional sites are: site 1: g1=1.9800, g2=1.9774, g3=1.9296, A1=7.25 mT, A2=8.09 mT, A3=18.69 mT and site 2: g1=1.9802, g2=1.9765, g3=1.9296, A1=6.82 mT, A2=8.48 mT, A3=18.75 mT, respectively. Superhyperfine, from protons of ligand water molecules, has been observed at certain orientations. It has been concluded that VO bond directions of the two substitutional ions are orthogonal to each other. 相似文献
9.
10.
Deprotonation of the nitrogen atoms of the two pyrrole rings of 1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyl}benzene with KH followed by further reaction with either VCl 3(THF) 3 or with VCl 2(TMEDA) 2 respectively gave the paramagnetic complexes [1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyl}benzene]VCl(DME) ( 1) and [1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyl}benzene]V(THF) 3 ( 2). Further reduction with the appropriate amount of KH afforded diamagnetic dinuclear [1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyl}benzene]V} 2] ( 3). In complex 3, the bridging interaction between the two metal centers is realized via the ligand central benzene ring. Density functional theory calculations have elucidated the nature of the electronic interaction between the two metals with the bridging pi-system thus accounting for its visible structural distortion. Calculations also pointed out the presence of only a weak V-V bond in spite of the short V-V distance. 相似文献
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