Cobalt--zinc molybdates as new blue pigments involving Co<sup>2+</sup> in distorted trigonal bipyramids and octahedra
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | ROBERTSON, Lionel | |
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | DUTTINE, Mathieu | |
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | GAUDON, Manuel | |
| hal.structure.identifier | Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB] | |
| dc.contributor.author | DEMOURGUES, Alain | |
| dc.date.issued | 2011 | |
| dc.identifier.issn | 0897-4756 | |
| dc.description.abstractEn | Zn<sub>1-<i>x</i></sub>Co<sub><i>x</i></sub>MoO<sub>4</sub> (<i>x</i> < 0.3) compounds prepared by the solid-state route crystallize in a triclinic unit cell with the <i>P</i>t space group. X-ray diffraction and Rietveld analyses reveal the occurrence of three highly distorted sites with equal occupancies corresponding to one trigonal bipyramidal CoO<sub>5</sub> group and two octahedral CoO<sub>6</sub> groups occupied by either Zn<sup>2+</sup> or Co<sup>2+</sup>. Mo<sup>6+</sup> 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 <i>g</i> values. The UV-vis spectra exhibit intense Co<sup>2+</sup> d-d transitions associated with CoO<sub>5</sub> and CoO<sub>6</sub> 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 MoO<sub>4</sub> entities and polarizable Zn<sup>2+</sup> cations creating highly distorted noncentrosymmetric sites partially occupied by Co<sup>2+</sup> allows stabilization of the first blue pigment without Co<sup>2+</sup> 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. | |
| dc.language.iso | en | |
| dc.publisher | American Chemical Society | |
| dc.subject | Cobalt | |
| dc.subject | Molybdates | |
| dc.subject | Structure | |
| dc.subject | Local environments | |
| dc.subject | d−d transitions | |
| dc.subject | Blue pigment | |
| dc.title.en | Cobalt--zinc molybdates as new blue pigments involving Co<sup>2+</sup> in distorted trigonal bipyramids and octahedra | |
| dc.type | Article de revue | |
| dc.identifier.doi | 10.1021/cm200795p | |
| dc.subject.hal | Chimie/Matériaux | |
| bordeaux.journal | Chemistry of Materials | |
| bordeaux.page | 2419-2427 | |
| bordeaux.volume | 23 | |
| bordeaux.issue | 9 | |
| bordeaux.peerReviewed | oui | |
| hal.identifier | hal-00593858 | |
| hal.version | 1 | |
| hal.popular | non | |
| hal.audience | Internationale | |
| hal.origin.link | https://hal.archives-ouvertes.fr//hal-00593858v1 | |
| bordeaux.COinS | ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chemistry%20of%20Materials&rft.date=2011&rft.volume=23&rft.issue=9&rft.spage=2419-2427&rft.epage=2419-2427&rft.eissn=0897-4756&rft.issn=0897-4756&rft.au=ROBERTSON,%20Lionel&DUTTINE,%20Mathieu&GAUDON,%20Manuel&DEMOURGUES,%20Alain&rft.genre=article |
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