Non-equivalence Magnetique en Resonance Nucleaire—IV. Influence de Plusieurs Types de Dissymetries sur les Deplacements Chimiques et les Couplages Relatifs a des Systemes ?O?CH2?CH3 et ?S?CH2?CH3

Magnetic non-equivalence of methylenic protons in A? CH₂? CH₃ groups were studied for several types of compounds. Results are compared with respect (1) to the nature of heteroatom A:A = O and A = S and (2) to the structure of the local dissymmetry element: asymmetric carbon, ketal group and allenic system. Influence of substitution is discussed in relation to conformational problems. Furthermore a variation of the methylene geminal coupling constant with substituents of carbon α to OEt is observed.     

Effect of trivalent cation substitution for manganese upon ferromagnetism in Ln0.57Ca0.43MnO3 (Ln=Pr, Nd)

The substitution of small contents of trivalent cations for manganese in the oxides Ln_0.57Ca_0.43Mn_1−xM_xO₃ (Ln=Pr, Na) has been explored for M=Al, Ga, Fe, Cr, Sc, In. It is shown that similarly to Ba-doping, the M-doped Pr-manganites exhibit a great predisposition to ferromagnetism in a low magnetic field of 0.25 T, reaching ferromagnetic (FM) fractions of 85% for M=Ga and 100% for m=Cr, whereas in contrast only small FM fractions (∼8%) can be reached for the M-doped Nd-manganites. The great ability of both Pr and Nd manganites to exhibit ultrasharp steps at 2.5 K, at increasing magnetic field is also demonstrated. The different behaviors of the so-doped manganites are interpreted in terms of geometric effects (size of the A-sites cations and of the doping elements) and of electronic configurations and magnetic properties of the dopants.     

Contribution a l'etude des metallocenes : XXVIII. Reduction de cetones cycliques en series du ferrocene et du cymantrene. Etude de la stereospecificite. Assignation des configurations endo ou exo des alcools derives

The reduction of various 2,3-ferroceno-1-indanones and 1,2-(α-oxotetramethylene)-methylcymantrenes by metal hydrides or Grignard reagents is stereo-specific, except for LiAlH₄, the observed stereoselectivity being in all uses more than 95%. The endo configuration of the dominant alcohol is established from TLC, IR, RMN and mass data. These criteria for the assignment of the structure of these alcohols are shown to be general.     

Formation of pentagonal tunnels bordered with P2O7 groups in diphosphate tungsten bronzes (P2O4)2(WO3)2m: A HREM investigation

During the investigation of the phosphate bronzes (PO₂)₄(WO₃)_2m [MPTB_P] and K_x(P₂O₄)₂WO₃)_2m [DPTB_H] crystals of a new type were observed. HREM images of these crystals showed twinned ReO₃-type slabs the junction of which was parallel to the (102)_ReO3 plane. The proposed model identified the twin boundary as built from P₂O₇ groups involving the formation of pentagonal tunnels. The structure of this new type of extended defects is quite original: it corresponds to a new structural type named “diphosphate tungsten bronzes with pentagonal tunnels” [DPTB_P], for which no regular member could be synthesized. Image calculations were performed to confirm the junction model. Apart from the disordered stacking of the ReO₃-type slabs, very few defects were observed and shear planes were only obtained in reduced samples. This new structural type takes its place in the large family of phosphate tungsten bronzes where all members (DPTB_H, MPTB_H, MPTB_P) are very closely related.     

Structural relationships in the series AxP4O8(WO3)2m (A = K,Rb): A high-resolution electron microscopy study

The first members of the series A_xP₄O₈(WO₃)_2m were studied by means of electron microscopy. These bronzes can be classified into two groups on the basis of ReO₃-type block composition: even- and odd-m members. High-resolution lattice images of tungstophosphate crystals (m ≤ 10) allow us to establish a correlation between the image contrast and the framework of the structure. The structural mechanism proposed for this series is discussed and compared to the possibility of intergrowth, and to the crystallographic shear phenomena observed in tungsten and molybden oxides.     

Pressure-induced structural transition in LuFe2O4: towards a new charge ordered state

The electronic ferroelectric lutetium ferrite (LuFe(2)O(4)) was studied by x-ray diffraction as a function of pressure. Pressure is shown to induce an irreversible rhombohedral to orthorhombic transition leading to a supercell determined by the combination of electron and synchrotron x-ray diffraction. This new configuration is proposed to be charge ordered in agreement with the results of resistivity measurements.     

Enhancement of magnetoresistance in cobaltites by manganese substitution: the oxide La 0.8 Sr 0.2 Co 1-x Mn x O 3

The substitution of manganese for cobalt in the perovskite La _0.8 Sr _0.2 CoO ₃ has been studied. A significant increase of the magnetoresistance (MR) is obtained, reaching 60% at 5 K under 7 T for . This behavior originates from a spectacular increase of the resistivity correlated to a significant decrease of ferromagnetism by Mn doping. This enhancement of magnetoresistance can be interpreted by the growth of ferromagnetic clusters in the insulating matrix, by applying a magnetic field. Received 7 May 1999     

Structural and magnetic phase diagram and room temperature CMR effect of La1−xAgxMnO3

The study of the structural and magnetic phase diagram of the manganites La_1−xAg_xMnO₃ shows similarity with the La_1−x′Sr_x′MnO₃ series, involving a metallic ferromagnetic domain at relatively high temperature (≈300 K). The Ag-system differs from the Sr-one by a much smaller homogeneity range (x≤1/6) and the absence of charge ordering. But the most important feature of the Ag-manganites deals with the exceptionally high magnetoresistance (−25%) at room temperature under 1.2 T, that appears for the composition x=1/6. The latter is interpreted as the coincidence of the optimal double exchange condition (Mn³⁺:Mn⁴⁺=2) with T_max=300 K (maximum of the ρ(T) curve in zero field).