ROBERTSON, Lionel; DUTTINE, Mathieu; GAUDON, Manuel; DEMOURGUES, Alain

doi:10.1021/cm200795p

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ROBERTSON, Lionel
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

DUTTINE, Mathieu
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

GAUDON, Manuel
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

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Chemistry of Materials. 2011, vol. 23, n° 9, p. 2419-2427

American Chemical Society

Résumé en anglais

Zn1-xCoxMoO4 (x < 0.3) compounds prepared by the solid-state route crystallize in a triclinic unit cell with the Pt space group. X-ray diffraction and Rietveld analyses reveal the occurrence of three highly distorted sites with equal occupancies corresponding to one trigonal bipyramidal CoO5 group and two octahedral CoO6 groups occupied by either Zn2+ or Co2+. Mo6+ ions are located in distorted tetrahedral sites. Electron paramagnetic resonance analysis allows characterization of the two kinds of environments with orthorhombic distortion related to two signals with different g values. The UV-vis spectra exhibit intense Co2+ d-d transitions associated with CoO5 and CoO6 chromophores between 1.9 and 2.6 eV in the visible domain and O-Mo charge transfer at the frontier between the UV and visible ranges. A blue-transmitted window can then be displayed. The formation of covalent MoO4 entities and polarizable Zn2+ cations creating highly distorted noncentrosymmetric sites partially occupied by Co2+ allows stabilization of the first blue pigment without Co2+ in the tetrahedral environment. Moreover, only 5-10% cobalt is necessary to get a strong blue hue because of the highly distorted sites leading to very important oscillator strengths.< Réduire

Mots clés

Cobalt

Molybdates

Structure

Local environments

d−d transitions

Blue pigment

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Cobalt--zinc molybdates as new blue pigments involving Co<sup>2+</sup> in distorted trigonal bipyramids and octahedra

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