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A Sr analogue of Ca0.5Bi0.5FeO3, Sr0.5Bi0.5FeO3, containing unusually high valence Fe3.5+ ions was synthesized by using a high-pressure technique. It relieves the electronic instability due to the unusually high valence of Fe3.5+ by a single charge disproportionation (CD) transition (Fe3.5+ -> 0.75Fe(3+) + 0.25Fe(5+)) rather than the successive CD and intermetallic charge transfer (CT) transitions seen in Ca0.5Bi0.5FeO3. Conduction-band narrowing due to the significant bend in the Fe-O-Fe bond in the rhombohedral R (3) over barc crystal structure stabilized the charge-disproportionated state at low temperatures. Most importantly, Bi3+ ions in Sr0.5Bi0.5FeO3 do not act as countercations accepting oxygen holes as they do in Ca0.5Bi0.5FeO3, resulting in the absence of the intermetallic CT transition. The large cavity of the A-site Sr ions prevents the charge-transferred Bi5+ from being stabilized. In the charge-disproportionated state the nearest-neighbor Fe3+ spins align antiferromagnetically and one-fourth of the Fe3+ spins are randomly replaced by Fe5+ spins coupled ferromagnetically with the neighboring Fe3+ spins.

The coupling between spins and charge disproportionation states has been investigated in the LaCa2Fe3O9 oxide with neutron powder diffraction. This A-site layer ordered triple perovskite LaCa2Fe3O9 undergoes charge disproportionation on cooling and shows two different charge ordering patterns. At 230 K, Fe3.67+ disproportionates into a 2:1 ratio of Fe3+ : Fe5+, which order in a layered manner along the direction of the pseudocubic unit cell. At lower temperatures (T direction. Neutron powder diffraction data show that in the intermediate temperature range (170 K layered magnetic structure.

The perovskite Ca0.5Bi0.5FeO3 undergoes a remarkable sequence of charge-disproportionation (CD) and charge-transfer (CT) transitions on cooling due to competing electronic instabilities: Ca0.5Bi0.53+Fe3.5+O3 -> Ca0.5Bi0.53+Fe0.673+Fe0.334.5+O3 (CD phase) -> Ca0.5Bi0.253+Bi0.255+Fe3+O3 (CT phase). The accompanying changes in charge and spin ordering have been determined from neutron diffraction and physical property measurements. The CT phase adopts a simple G-type antiferromagnetic structure of Fe3+ spins but the CD phase adopts an unusual charge and magnetic arrangement in which Fe3+ spins are antiferromagnetically ordered but the Fe4.5+ moments have no long-range order due to magnetic frustration and form a spin glass at low temperatures.

Ce mémoire concerne l'influence d'un degré d'oxydation inusuel d' un element de transition (Cu(III), Cu(IV), Fe(IV)) sur les proprietes physico-chimiques des réseaux oxygènes dérivés de structure perovskite. Les différentes structures du compose du cuivre trivalent LaCuO3 (formes basse et haute pression) ont été étudiées. Le role de plusieurs facteurs sur les propriétés physiques de ce matériau a pu etre mis en évidence, en particulier: 1) l'accroissement de la covalence moyenne de la liaison Cu-O du a la stabilisation de la valence mixte Cu(III)/Cu(IV) obtenue par substitution du Sr au La; 2) la distorsion structurale induite par substitution de l'yttrium au lanthane; 3) la pression d'oxygène de synthèse. La seconde partie de ce travail permet, au travers d' une étude Mössbauer par sonde diamagnétique locale (119Sn), d' expliquer le mécanisme de dismutation du fer tétravalent au sein d'un réseau perovskite AFeO3 (A=Ca, Sr); non disponible

We consider magnetic ordering in materials with negative charge transfer energy, such as iron perovskite oxides. We show that for a large weight of oxygen holes in conduction bands, the double exchange mechanism favors a helicoidal rather than ferromagnetic spin ordering both in metals, e.g. SrFeO_3 and insulators with a small gap, e.g. CaFeO_3. We discuss the magnetic excitation spectrum and effects of pressure on magnetic ordering in these materials., Comment: 4 pages, 5 figures