Synthesis and thermal decomposition of a novel zirconium acetato-propionate cluster: [Zr12]

• Published in: Solid state sciences 2011-03, Vol.13 (3), p.665-670
• Main Authors: Petit, Sarah, Morlens, Stéphanie, Yu, Zeming, Luneau, Dominique, Pilet, Guillaume, Soubeyroux, Jean-Louis, Odier, Philippe
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Chemical solution deposition; Chemical synthesis methods; Clusters; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Decomposition; Derivatives; Diffraction; Exact sciences and technology; La 2Zr 2O 7; Low-dimensional structures (superlattices, quantum well structures, multilayers): structure, and nonelectronic properties; Material chemistry; Materials science; Methods of nanofabrication; MOD; Molecular structure; Other materials; Physics; Propionates; Propionic acid; Specific materials; Surfaces and interfaces; thin films and whiskers (structure and nonelectronic properties); X-rays; Zirconium; Zirconium cluster; Zirconium dioxide
• ISSN: 1293-2558; 1873-3085
• DOI: 10.1016/j.solidstatesciences.2010.12.041

This work reports a novel Zirconium acetato-propionate complex herein called [Zr12] obtained by reaction of zirconium acetylacetonate Zr(acac) 4 with propionic acid. The molecular structure has been determined by X-ray diffraction on single crystals and proposed to be [Zr 12(μ 3-O) 16(CH 3CH 2CO 2) 12(CH 3CO 2) 8(μ 2-CH 3CH 2CO 2) 4]. This cluster involves oxo/hydroxo bonds in the direct surrounding of the metallic center. The decomposition of [Zr12] has been studied by thermal analysis and compared to Zr(acac) 4. Its temperature of decomposition is much lower than for acetylacetonate derivative. In consequence, the formation of ZrO 2 is easier from [Zr12] than from Zr(acac) 4. This phenomenon highlights the influence of the molecular structure on the process of decomposition. The local surrounding of Zr in [Zr12] and in ZrO 2 are very close, while it is markedly different in Zr(acac) 4.This difference of environment of the metallic ions is at the origin of the huge difference of thermal behavior of both compounds. [Display omitted]