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The Instituto de Ciencia de Materiales de Madrid (ICMM) is an institute of the Consejo Superior de Investigaciones Cientificas (CSIC) (Spanish National Research Council) founded in December 1986, that belongs to the Area of Science and Technology of Materials, one of the eight Areas in which the CSIC divides its research activities.


Our mission is to create new fundamental and applied knowledge in materials of high technological impact, their processing and their transfer to the productive sectors at local, national and European scales (the true value of materials is in their use), the training of new professionals, and the dissemination of the scientific knowledge.

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Hydroxyapatites as Versatile Inorganic Hosts of Unusual Pentavalent Manganese Cations

Varela A., Gómez-Recio I., Serrador L., Hernando M., Matesanz E., Torres-Pardo A., Fernández-Díaz M.T., Martínez J.L., Gonell F., Rousse G., Sanchez C., Laberty-Robert C., Portehault D., González-Calbet J.M., Par

Contrary to molecular species, only very few solids are reported to host manganese (V) species. Herein, we report three new compounds with a hydroxyapatite structural backbone built on the MnVO43– anion: Sr5[(Mn1–xSix)O4]3(OH)1–3x (x = 0 and 0.053), Sr5(MnO4)3(OH)1–yFy (y = 0.90), and Sr5[(Mn1–xSix)O4]3F1–3x (x = 0.058). These solids are fully characterized using powder X-ray and neutron powder diffraction, scanning transmission electron microscopy, electron energy loss spectroscopy (EELS), thermogravimetric analysis, and magnetic measurements. Especially, we report for the first time EELS Mn–L2,3 spectra of manganese with the oxidation state (V). Contrary to other Mn(V) oxides, these solids and the nominal compound Sr5(MnO4)3OH do not comprise Ba2+ cations but rely only on Sr2+ cations, showing that barium is not a required element to stabilize Mn(V) species in inorganic solids. We show that by tuning soft chemistry conditions on the one hand and post-treatment topological transformation conditions on the other hand, Mn(V) and hydroxyl groups can be substituted by Si(IV) and fluoride ions, respectively. Hence, we deliver solids with a potentially wide composition range. These compounds show significant oxygen anionic conduction, thus suggesting the emergence of new functional materials built from high-oxidation state manganese cations.

Chemistry of Materials

Apatite Ca5(PO4)3X-type structure (X: OH, F, or Cl). On the right are shown the two coordinations for Ca: nine-coordinated CaO9 tricapped trigonal prisms and a seven-coordinated one forming AO6X bicapped trigonal prisms.

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