Intercalation d'ions metallicinium dans les gels de V2O5

Cobalticinium and ferricinium cations have been intercalated at room temperature into the lamellar structure of V₂O₅ gels. In both cases an almost constant basal d-spacing is observed, about 13.2 Å whatever the counterion used. The basic V₂O₅ ribbon structure is not modified upon intercalation, but noticeable improvement of the order along the ribbon packing direction is obtained, especially with Co(C₅H₅)⁺₂. The 4.4 Å increase in the basal d-spacing and its high temperature evolution allow to deduce that cyclopentadienyl rings interpenetrate the V₂O₅ ribbons presumably in the usual perpendicular position. Water is involved in the intercalation mechanism which is likely of the exchange type rather than of the redox type. Intercalate formula is approximately V₂O₅, 0.4 Fe(C₅H₅)₂, x H₂O (with x < 0.5). The materials, especially the Co(C₅H₅)⁺₂ intercalate, are still stable beyond 200°C. Such a high thermal stability is quite remarkable.