CaMn4O8, a mixed valence manganite with an original tunnel structure

A new mixed valent manganite CaMn4O8 with an original tunnel structure has been synthesized. The host lattice of this oxide has been determined by X-ray powder diffraction, using ab initio methods, and by high resolution electron microscopy. It consists of single and triple chains of edge-sharing MnO6 octahedra, interconnected through their apices. The [Mn4O8](infinity) framework delimits three types of tunnels: six-sided ("H") and eight-sided ("8") where sit the Ca2+ cations, and empty rutile-like tunnels ("R"). The analysis of the Mn-O inter-atomic distances shows that this structure could also be described from the association of only single chains of edge-sharing MnO6 octahedra, with single chains of edge-sharing MnO5 pyramids, and evidences a high tendency of manganese to charge ordering. Nanostructural mechanisms investigated by electron microscopy also allow the structure to be described in terms of single bricks of four Mn polyhedra, and evidence twinning and intergrowth phenomena as well as local ordering of calcium in the tunnels. The magnetic measurements show strong antiferromagnetic fluctuations at low temperature, whereas the low value of T-N similar to 90 K indicates that the antiferromagnetic superexchange is weak in this oxide.