Structure-toxicity relationships of thiono and seleno phosphoramidate compounds: new type of acetylcholinesterase inhibitors

Novel thiono and seleno phosphoramidate compounds with the general formula (X)(Y)P(C₆H₅)₂; (X = NMe₂ & Y = S, 1a; X = NEt₂ & Y = S, 2a; X = NMe(CH₂Ph) & Y = S, 3a; X = NH(CH₂Ph) & Y = S, 4a; X = NEt(CH₂Ph) & Y = S, 5a; X = N(C(Me)₃) (CH₂Ph) & Y = S, 6a; X = N(CH₂Ph)₂ & Y = S, 7a; X = NMe₂ & Y = Se, 1b; X = NEt₂ & Y = Se, 2b; X = NMe(CH₂Ph) & Y = Se, 3b; X = NH (CH₂Ph) & Y = Se, 4b; X = NEt(CH₂Ph) & Y = Se, 5b; X = N(C(Me)₃)(CH₂Ph) & Y = Se, 6b and X = N(CH₂Ph)₂ & Y = Se, 7b) were prepared and characterized by ¹H, ³¹P and ¹³C NMR and IR spectroscopy and elemental analysis. ³¹P chemical shift of thiono and seleno derivatives didn’t show significant different because of their little difference in electronegativity sulfur and selenium. Hydrophobic parameter of compounds was determined by measurement of octanol-water partition coefficient by shake-flask technique. Determination of human erythrocyte acetylcholinesterase (hAChE) activity was carried out according to the Ellman’s modified kinetic method. IC₅₀ values of the selected thiono and seleno compounds varied from 3.4 to 0.11 and 9.9 to 5.1 mM, respectively. The seleno compounds show lower affinities for hAChE relative to the thino compounds. These results demonstrate that hydrophobic and electronic factors of the organophosphorus compounds play a key role on the inhibitory potency.     

Effects of Ca substitution on the phonon anomalies in the Raman scattering of YBa<Subscript>2</Subscript>Cu<Subscript>4</Subscript>O<Subscript>8</Subscript>

We report on the temperature dependence of the frequencies and linewidths in the phonon Raman scattering for Y _1-y Ca y Ba ₂ Cu ₄ O ₈ system ( y = 0 - 0.15). The phonon anomalies above T _c of the frequencies are observed for the out-of-phase O(2)-O(3) A _g and O(4) A _g modes, and these onset temperatures decrease with increasing Ca content. These features are consistent with the spin-gap behaviors associated with Ca doping reported previously. Furthermore, we find that the smaller gap exists near or just above the Ba phonon frequency at in the undoped samples and its energy increases with Ca doping. Received 9 June 1999     

81Br NQR Study of [NH3(CH2) n NH3]CdBr4 (n = 4 and 5) and [NH3(CH2) n NH3]ZnBr4 (n = 5 and 6)

⁸¹Br NQR frequencies and differential scanning calorimetry (DSC) were measured as a function of temperature. [NH₃(CH₂)₄ NH₃]CdBr₄ (1) and [NH₃(CH₂)₅NH₃]CdBr₄ (2) showed a doublet and quartet ⁸¹Br NQR spectrum, respectively. [NH₃(CH₂)₅NH₃]ZnBr₄ (3) and [NH₃(CH₂)₆NH₃]ZnBr₄ (4) exhibited a four-line ⁸¹Br NQR spectrum. From the NQR results, it is inferred that (1) and (2) consist of infinite two-dimensional sheets of corner-sharing CdBr₆ octahedra, whereas (3) and (4) have isolated [ZnBr₄]²⁻ tetrahedra. All of the crystals except (1) showed at least one structural phase transition above 380 K.     

Interplay of structural, magnetic and transport properties in thelayered Co-based perovskite LnBaCo 2 O 5 (Ln = Tb, Dy, Ho)

The oxygen deficient cobaltites LnBaCo₂O₅ (Ln = Tb, Dy, Ho) exhibit two successive crystallographic transitions at T _N ∼340 K and at T _CO ∼210 K. Whereas the first transition (P4/mmm to Pmmm) is related to the long-range antiferromagnetic ordering of the Co ions (spin ordering), the second transition (Pmmm to Pmmb) corresponds to the long-range ordering of the Co²⁺ and Co³⁺ species (charge ordering) occurring in 1:1 ratio in the structure. The charge ordered (CO) state was directly evidenced by the observation of additional superstructure peaks using neutron and electron diffraction techniques. The CO state was also confirmed indirectly from refinement of high resolution neutron diffraction data as well as from resistivity and DSC measurements. From the refined saturated magnetic moment values only, ∼3.7 and ∼2.7 , the electronic configuration of the Co ions in LnBaCo₂O₅ remains conjectural. Two pictures, with Co³⁺ ions either in intermediate spin state ( t ⁵ _2g e ¹ _g ) or in high spin state ( t ⁴ _2g e ² _g ), describe equally well our experimental data. In both cases, the observed magnetic structure can be explained using the qualitative Goodenough-Kanamori rules for superexchange. Finally, in contrast to the parent Ln = Y compound [Vogt et al. , Phys. Rev. Lett. 84, 2969 (2000)], we do not report any spin transition in LnBaCo₂O₅ (Ln = Tb, Dy, Ho). Received 13 December 2000     

Elastic anomalies and orientational glass transition in Na(CN) Cl mixed crystals. A Brillouin spectroscopic study

High performance Brillouin spectroscopy (BS) has been used to study the elastic properties (static and dynamic) of the orientational glassy state of Na(CN)_xCl_1-x samples ). The temperature behaviour of the elastic properties reveals a more complex scenario for the orientational glass transition than generally believed. The shear elastic constant shows the well-known c ₄₄ ( T ) anomaly, indicated by a minimum, found in other cyanide mixed crystals. The results obtained for the hypersonic attenuation are in clear contradiction with the dynamic character of the c ₄₄ ( T )-minimum. The temperature behaviour of the longitudinal elastic constant c₁₁ of very dilute Na(CN)_xCl_1-x samples shows two striking features: i) Similar to the anomalous temperature behaviour of c ₄₄ ( T ), lowering the temperature c ₁₁ ( T ) first decreases, goes through a minimum and then rises again. The minimum takes place at a temperature above the temperature, , where c ₄₄ ( T ) reaches its minimum value. ii) A kink-like anomaly of c ₁₁ ( T ) is observed at lower temperatures. This second anomaly is similar to the classical one observed in canonical glasses at their glass transition temperature . Received 8 April 1999 and Received in final form 3 June 1999     

Dimer dissociation energies of small odd-size clusters

The dimer dissociation energies of gold cluster ions Au ⁺ _n , n = 9, 11, 13, 15 have been determined with an extension of a recently developed model-independent method. Monomer-dimer decay pathway branching ratios provide the energy dependent process which is needed in this method. The measured values are D ₂ ( Au ⁺ ₉ ) = 3.66(8)(9) eV, D ₂ ( Au ⁺ ₁₁ ) = 4.27(11)(8) eV, D ₂ ( Au ⁺ ₁₃ ) = 4.50(9)(7) eV and D ₂ ( Au ⁺ ₁₅ ) = 4.29(10)(6) eV. Received 13 May 2002 / Received in final form 22 July 2002 Published online 24 September 2002 RID="a" ID="a"e-mail: manuel.vogel@uni-mainz.de     

The effect of ligands on the first hyperpolarizabilities of rich d electron molecular system: iridium clusters,a TDDFT study

A systematically varied series of tetrahedral iridium clusters have been studied using a TDDFT method focusing on their electronic and nonlinear optical properties. The clusters W₂Ir₂(CO)₁₀(η⁵-C₅H₄Me)₂ (1), WIr₃(μ-dppe)(CO)₉(η⁵-C₅H₄Me (2), W₂Ir₂(μ-L)(CO)₈(η⁵-C₅H₄Me)₂(L = dppe 3, dppf 4), Ir₄(μ-L)(CO)₁₀(L = dppm 5, dppe 6, Ph₂P(CH₂)₃PPh₂ 7, Ph₂P(CH₂)₄PPh₂ 8, (Ph₂P)₂CHMe 9), Ir₄(CO)₁₀(phen)(phen = 1,10-phenanthroline) (10) exhibit the first static hyperpolarizabilities of medium magnitude (β _tot ～ 10 × 10^?30esu). The origination of β is discussed in terms of the electronic structure calculation and the expanded orbital decomposition scheme. The result suggests the origination of β for all the clusters are mainly d–d electron transitions intra metal skeleton, and d–π* electron transitions from metals to carbonyls. For cluster 5, which contains the ferrocenyl group, the main origination of β involves charge transfer from d orbitals of ferrocene to d orbirals of Ir and W.     

Double-stranded helical lanthanide(III) supramolecular networks with rigid diimine ligands: Synthesis, structure, and physical properties

Two lanthanide coordination complexes [Nd(NO₃)₃(CH₃OH)₂(4,4′-bipy)₂] (1) (4,4′-bipy=4,4′-bipyridine) and [4,4′-Hbipy][La(NO₃)₄(H₂O)₂(4,4′-bipy)] (2), with a salt of cationic diprotonated 4,4′-bipy, [2(4,4′-H₂bipy)][4(NO₃)] (3), have been identified and isolated from a methanol solution of Ln(NO₃)₃·6H₂O, 4,4′-bipyridine and pyrazine in 1:2:1 ratio. Their structures have been determined by single-crystal X-ray diffraction analyses, which reveal that 1 has an interesting three-dimensional supramolecular architecture containing 2₁ double-stranded helical chains through hydrogen bonding and π–π interactions, while 2 and 3 have well defined infinite chiral 3D open networks that undergo self-interpenetration. The electrospray ionization mass spectra (ESI-MS) indicate that the covalent complex has higher stability than the electrostatic bonding one. ESI-MS/MS of these ions reveal that the Ln–O bond forms a stronger coordinated bonding than that of Ln–N system and the nitrate anion remains bound to the lanthanide centers after complete dissociation in methanol solution.     

On the existence of <Emphasis Type="Bold">1, 3</Emphasis>P <Emphasis Type="Bold">o</Emphasis> resonances in H<Superscript>-</Superscript> between n = 2 and 3 H thresholds

We examine the influence of relativistic and QED effects on the existence of the ^1,3P ^o H^- resonances between n = 2 and 3 hydrogen thresholds, the relativistic and QED corrections and the coupling effects between the high singlet and triplet states are considered as first-order perturbations. We firstly obtain accurate non-relativistic resonant energies and widths of fifteen ¹P ^o resonances, and fifteen ³P ^o resonances. The fifteen ¹P ^o resonances are classified to be ₃ (2, 0) ^- _n ( 4 ? n ? 12) and ₃ (1, 1) ⁺ _n ( 3 ? n ? 8). The fifteen ³P ^o resonances are classified to be ₃ (2, 0) ⁺ _n ( 3 ? n ? 12) and ₃ (1, 1) ^- _n ( 4 ? n ? 8). We found there exist six Feshbach resonances for ₃ (2, 0) ^- _n (¹P ^o ) series, four Feshbach resonances for ₃ (1, 1) ⁺ _n (¹P ^o ) series, seven Feshbach resonances for ₃ (2, 0) ⁺ _n (³P ^o ) series, and three Feshbach resonances for ₃ (1, 1) ^- _n (¹P ^o ) series. Received 22 February 2002 Published online 24 September 2002     

Conformational analysis of <Emphasis Type="Italic">o</Emphasis>-allylphenol by density functional and IR spectroscopy methods

The two-dimensional cyclic potential energy surfaces for internal rotation of the allyl substituent and its vinyl fragment in o-allylphenol (o-APh) depending on the OH group orientation relative to the allyl substituent were constructed by a B3LYP/6-31G method. It is shown that o-APh exists in the gas phase as a mixture of eight non-planar rotamers (A, B, C, D, E, F, G, and H) and their eight optical isomers (A ₁, B ₁, C ₁, D ₁, E ₁, F ₁, G ₁, and H ₁). An intramolecular H-bond (IHB) O–H...π occurs only in four rotamers (A, B, A ₁, and B ₁). The content of such rotamers in the gas phase is 47.2% (as calculated by the B3LYP/cc-pVTZ method). Taking into account the solvation effect in the polarizable continuum model (PCM) for a solution of o-APh in cyclohexane decreases the total content of rotamers with an IHB (A and B) to 37.7%. The ratio of rotamers with OH groups bonded by an IHB and with free OH groups that is predicted theoretically agrees with the value measured experimentally from IR spectra of o-APH in CCl₄ solution.     

Resonance Raman excitation and electronic structure of the single bonded dimers (C ¯60)2 and (C 59N)2

Raman spectra are presented for the single bonded dimeric fullerene (C ₆₀ ^- ) ₂ and compared to optical spectra and Raman spectra of the isostructural and isoelectronic heterofullerene (C₅₉N)₂. The spectra of both materials exhibit strong correlations with respect to splitting, line position, and line intensity. This holds for non resonant excitation with blue and green lasers as well as for the strong resonances observed with red lasers. The latter observation is consistent with a downshift for the electronic transition energies as compared to C₆₀. The absorption edge of thin films of (C₅₉N)₂ was found at 1.4 eV. The three intercage modes were observed at 82, 103, and 111, and at 88, 98, and 106 cm^-1 for (C₅₉N)₂ and (C ₆₀ ^- ) ₂ , respectively. A surprising difference was found for the position of the pentagonal pinch modes in the two materials as they were observed at 1461 and at 1451 cm^-1, for (C₅₉N)₂ and (C ₆₀ ^- ) ₂ , respectively. This is interpreted as a consequence of some characteristic differences in the electronic structure of the two compounds. Received 25 January 2000 and Received in final form 10 April 2000     

Finestructure, hyperfine structure and isotope shift of 4f 6s7s in Er I

The isotope shift (IS) and hyperfine structure (hfs) of nine levels (31720 to 38921 cm^-1) assigned to the configuration 4 f ¹² 6 s 7 s in neutral erbium have been determined experimentally using Doppler-reduced saturation absorption spectroscopy in a gas discharge. We performed a fine structure analysis in the SL-coupling scheme of the single configuration 4 f ¹² 6 s 7 s, confirming and extending the classification of even parity Er I levels. We discriminated the different hfs contributions of the 4f¹² core and the (6 s +7 s) outer electrons of the shell in a non-relativistic JJ-coupling approach and in the relativistic effective tensor operator formalism in SL-coupling. The relativistic one-electron parameters of the hfs for ¹⁶⁷Er were fitted to the experimental data by a least squares fit procedure: [0pt] a ⁰¹ _4f =-147(3) MHz, [0pt] a ¹⁰ _6s + a ¹⁰ _7s =-1840(30) MHz, [0pt] b ⁰² _4f =6560(80) MHz. The level dependencies of the isotope shift were evaluated based on crossed second order (CSO) effects. We obtained the following results for the CSO parameters for the isotope pairs ^170-168Er: d _6s7s =-740(30) MHz, z _4f = 0(5) MHz, ( g _3,6s ( f , 6 s )+ g _{3, 7s} ( f , 7 s ))= -24(15) MHz and for ^170-166Er: d _6s7s =-1500(50) MHz, z _4f =0(10) MHz, ( g _3,6s ( f ,6 s )+ g _3,7s ( f +7 s ))=-50(29) MHz. The resulting parameters for the hfs are compared with those known for other configurations of the Er atom and ion. Received 16 May 1999 and Received in final form 31 January 2000     

The structural transformation of monoclinic [(R)-C5H14N2][Cu(SO4)2(H2O)4]·2H2O into orthorhombic [(R)-C5H14N2]2[Cu(H2O)6](SO4)3: crystal structures and thermal behavior

Single crystals of [(R)-C₅H₁₄N₂][Cu(SO₄)₂(H₂O)₄]·2H₂O (1) were grown through the slow evaporation of a solution containing H₂SO₄, (R)-C₅H₁₂N₂ and CuSO₄·5H₂O. These crystals spontaneously transform to [(R)-C₅H₁₄N₂]₂[Cu(H₂O)₆](SO₄)₃ (2) over the course of four days at room temperature. The same single crystal on the same mounting was used for the determination of the structure of (1) and the unit cell determination of (2). A second single crystal of the transformed batch has served for the structural determination of (2). Compound 1 crystallizes in the noncentrosymmetric space group P2₁ (No. 4) and consists of trimeric [Cu(SO₄)₂(H₂O)₄]^2? anions, [(R)-C₅H₁₄N₂]²⁺ cations and occluded water molecules. Compound 2 crystallizes in P2₁2₁2 (No. 18) and contains [Cu(H₂O)₆]²⁺ cations, [SO₄]^2? anions and occluded water molecules. The thermal decompositions of compounds 1 and 2 were studied by thermogravimetric analyses and temperature-dependent X-ray diffraction.     

Thermal conductivity and thermal Hall effect in Bi- and Y-based high-T c superconductors

Measurements of the thermal conductivity (k_xx) and the thermal Hall effect (k_xy) in high magnetic fields in Y- and Bi-based high-T _c superconductors are presented. We describe the experimental technique and test measurements on a simple metal (niobium). In the high-T _c superconductors k_xx and k_xy increase below T _c and show a maximum in their temperature dependence. k_xx has contributions from phonons and quasiparticle (QP) excitations, whereas k_xy is purely electronic. The strong increase of k_xy below T _c gives direct evidence for a strong enhancement of the QP contribution to the heat current and thus for a strong increase of the QP mean free path. Using k_xy and the magnetic field dependence of k_xx we separate the electronic thermal conductivity ( k _xx ^el ) of the CuO ₂ -planes from the phononic thermal conductivity ( k _xx ^ph ). In YBa₂Cu₃O _{7 - δ} k _xx ^el shows a pronounced maximum in the superconducting state. This maximum is much weaker in Bi₂Sr₂CaCu₂O _{8 + δ} , due to stronger impurity scattering. The maximum of k _xx ^el is strongly suppressed by a magnetic field, which we attribute to the scattering of QPs on vortices. An additional magnetic field independent contribution to the maximum of k_xx occurs in YBa₂Cu₃O _{7 - δ} , reminiscent of the contribution of the CuO-chains, as determined from the anisotropy in untwined single crystals. Our data analysis reveals that below T _c as in the normal state a transport (τ) and a Hall ( ) relaxation time must be distinguished: The inelastic (i.e. temperature dependent) contribution to τ is strongly enhanced in the superconducting state, whereas displays the same temperature dependence as above T _c . We determine also the electronic thermal conductivity in the normal state from k_xy and the electrical Hall angle. It shows an unusual linear increase with temperature. Received 23 August 2000     

Energy loss of 18 keV electrons in gaseous T and quench condensed D films

Measurements of the energy loss of fast electrons at an energy of 18 keV have been performed on molecules of hydrogen isotopes, gaseous T ₂ and frozen D ₂ . Whereas in the case of gaseous T ₂ the values of total inelastic cross-section ( cm² for E = 18.6 keV), average energy loss ( eV) and peak position of the energy loss spectra ( eV) agree well with the expectations, the corresponding values for quench condensed D ₂ differ significantly from the ones for gaseous T ₂ . We observe a significant lower total inelastic cross-section ( cm², for E = 18.6 keV) larger average energy loss ( eV) and higher peak position ( eV). These differences may be interpreted in terms of changes of the final state spectrum. A CI calculation for a D ₂ cluster shows indeed a clear shift of the excited states in agreement with the observation. Received 24 August 1999     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Mexiletine

The 60 MHz ¹H NMR spectra of mexiletine, 1-(2,6-dimethylphenoxy)-2-propanamine, 1, have been studied at 28° in CDCl₃ solution with the achiral reagent, tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium(III), 2, Eu(FOD)₃, and the chiral reagents tris[3-(trifluoromethylhydroxymethylene)-d-camphorato]europium(III), 3, Eu(FACAM)₃, and tris[3-(heptafluoropropylhydroxymethylene)-d-camphorato]europium(III), 4, Eu(HFC)₃. Substantial lanthanide-induced shifts were seen for the proton signals of 1 with each reagent. Appreciable enantiomeric shift differences were seen for both methyl signals and for each of the CH₂CH proton signals using 3 and 4 that should permit direct determinations of enantiomeric excess for samples of 1. A predominant conformation for 1 is suggested based on observed splittings of the CH₂ proton signals and their relative lanthanide-induced shifts.     

Theoretical study on the influence of different NˆN ligands on the electronic structures and optoelectronic properties of heteroleptic Iridium(III) complexes

DFT/TDDFT calculations were carried out to investigate the electronic structures, absorption and phosphorescence properties of a series of heteroleptic Ir(III) complexes consisting of two N-heterocyclic carbene ligands and a conjugated bicyclic N,N′-heteroaromatic (N?N) ligand. On the basis of the results reported herein, we attempt to explain the experimental observations according to which complex (mpmi)₂Ir(pybi) (1) [Hmpmi = 1-(4-tolyl)-3-methyl-imidazole; Hpybi = 2-(pyridin-2-yl)-1H-benzo[d]imidazole] emits green light with an extremely high-quantum phosphorescence efficiency (Φ _PL ) of 79.3%, while a relatively lower Φ _PL (only 11%) was measured for (fpmi)₂Ir(tfpypz) (2) [fpmi = 1-(4-fluorophenyl)-3-methylimdazolin-2-ylidene-C, C^2′; tfpypz = 2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)pyridinato] emitting blue light by tuning the N?N ligands. Besides, we also designed (fpmi)₂Ir(pyN3) (3) [pyN3H = 2-(5-(trifluoromethyl)-2H-1,2,4-triazol-3-yl)pyridine] and (fpmi)₂Ir(pyN4) (4) [pyN4H = 2-(1H-tetrazol-5-yl)pyridine] to explore the influence of electron-withdrawing substituents on N?N ligands on the electronic and optical properties of these Ir(III) complexes. The results revealed that electron-withdrawing substituents can stabilise both HOMOs and LUMOs and induce HOMO–LUMO energy gap change. Moreover, the emission properties can be significantly tuned by introducing different N?N ligands. While new insights were gained on structural and electronic properties, the extremely high Φ _PL of 1 was found to be not inherent to spin-orbital coupling effects, but determined by its large transition dipole moment (μ_{S 1}) upon S ₀–S ₁ transition compared with that of 2. On the basis of these results, the designed complexes 3 and 4 are considered to be the promising candidates for blue-emitting phosphorescence materials with higher Φ _PL than the complex 2.     

High accuracy Dirac-finite-element (FEM) calculations for H 2 + and Th 2 179 +

A two-dimensional, fully numerical approach to the four-component first-order Dirac-differential-equation utilizing the Finite-Element-Method (FEM) is employed for H ₂ ⁺ and Th ₂ ^{179 +} . Using elliptic-hyperbolic coordinates and further one-dimensional singular transformations, scaling transformations and extrapolation techniques (geometrical over iteration steps and logarithmic over grid points) we achieve for the molecules H ₂ ⁺ and Th ₂ ^{179 +} relative accuracies better than 10^-12 for 1(1/2) g energies. Received 16 February 2001 and Received in final form 12 July 2001     

Polysilyl radicals: EPR study of the formation and decomposition of star polysilanes

Electron paramagnetic resonance (EPR) spectroscopy was fruitfully used for studying the formation and the reactions of the star polysilane radical (Me₃SiMe₂Si)₃Si (1).1, which was successfully generated both thermally and photochemically from a variety of precursors, was found to be significantly more stable kinetically than the (Me₃Si)₃Si radical. Thus, (Me₃SiMe₂Si)₃Si^⋅ has a half-life time of ca. 6 min at 20°C, while (Me₃Si)₃Si^⋅ can be observed only at −25°C. Density-functional quantum-mechanical calculations show that1 and (Me₃Si)₃Si^⋅ have the same thermodynamic stability. The high kinetic stability of1 is attributed to its backfold “umbrella”-type conformation where the β-silyl groups point “inwards” towards the radical center. This conformation protects the radical center of1 from dimerization and other reactions. The EPR spectrum of1 and in particular the Si α-hyperfine coupling constant of 5.99 mT shows that1 is less pyramidal than (Me₃Si)₃Si^⋅ but is more pyramidal than (i-Pr₃Si)₃Si^⋅, with an estimated SiSiSi bond angle around the radical center of 118∘. Photolysis and thermolysis of [(Me₃SiMe₂Si)₃Si]₂ also involves the intermediacy of1. Photolysis of [(Me₃SiMe₂Si)₃Si]₂ leads to (Me₃SiMe₂Si)₄Si, while thermolysis produced the less strained isomer of 1, (Me₃SiMe₂Si)₃SiSi-Me₂Si(Me₃SiMe₂Si)₂SiMe₃. In this study we provide the first direct evidence that silyl radicals are involved as intermediates in the reactions of silanes with di(tert-butyl)mercury.     

Preparation, magnetoresistance and magnetocaloric effect of two-layered perovskite La 2.5- x K 0.5+ x Mn 2 O 7+δ

Polycrystalline two-layered perovskite La_2.5-xK_0.5+xMn₂O _{7 + δ} (0 < x < 0.5) samples have been prepared by a modified sol-gel method and their magnetoresistance and magnetocaloric effects have been studied. A large deviation between the metal-insulator (MI) transition temperature (T _ρ ) and the magnetic transition temperature (T_C) is observed. Large magnetoresistance (MR) effects with Δρ/ρ of ∼40% at 12 kOe are obtained in wide temperature ranges. The maximum of the magnetic entropy change peaks at its Curie temperature (T_C), far above its MI transition temperature (T _ρ ). The large magnetic entropy change (∼1.4 J/kg.K) is obtained in the sample La_2.5-xK_0.5+xMn₂O _{7 + δ} (x = 0.35) upon 10 kOe applied magnetic field. Received 2 May 2002 / Received in final form 1st October 2002 Published online 19 December 2002 RID="a" ID="a"e-mail: wzhong@ufp.nju.edu.cn