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Influence of the lead carboxylate on the molecular composition of its solutions with zirconium and titanium isopropoxides or n-butoxides: 2-ethylhexanoate vs acetate, a way to stabilize the first Pb-Zr carboxylatoalkoxides of 1:1 stoichiometry

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Abstract

The reactions between titanium or zirconium alkoxides namely Ti(OR)4 (R = iPr, nBu) or Zr2(OiPr)8(HOiPr)2, Zr(OnBu)4 respectively and lead 2-ethylhexanoate Pb(O2CC7H15)2 were investigated at room temperature (rt) and by heating. The various compounds were characterized by elemental analysis, FT-IR, 1H and 207Pb NMR. The mixed-metal species obtained at rt were adducts Pb4Zr4(μ-O2CR′)8(OR)16(OHR)2 1 and Pb2Ti4(μ-O2CR′)4(OR)16 2 (R′=CHCHEt(CH2)2Me, R = iPr) independently of the stoichiometry used. The structures of 1 and 2 are based on triangular M2Pb cores (M = Zr, Ti). with 6-coordinate transition metals -as required for perovskites- and 6- or 7-coordinate lead atoms. Similar observations were made with n-butoxides. Thermal and hydrolytic condensation reactions were investigated. Thermal condensation was more difficult for the n-butoxide derivatives than for the isopropoxide ones. Powders derived from the hydrolysis of the Single Source Precursor 1 in various conditions were characterized by TGA, XRD and SEM for the PZ ceramic.

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  1. Université C. Bernard Lyon1, IRC, 2 Avenue A. Einstein, 69 626, Villeurbanne Cedex, France

    Anne Brethon & Liliane G. Hubert-Pfalzgraf

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  1. Anne Brethon
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  2. Liliane G. Hubert-Pfalzgraf
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Correspondence to Liliane G. Hubert-Pfalzgraf.

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Brethon, A., Hubert-Pfalzgraf, L.G. Influence of the lead carboxylate on the molecular composition of its solutions with zirconium and titanium isopropoxides or n-butoxides: 2-ethylhexanoate vs acetate, a way to stabilize the first Pb-Zr carboxylatoalkoxides of 1:1 stoichiometry. J Sol-Gel Sci Technol 39, 159–167 (2006). https://doi.org/10.1007/s10971-006-9169-x

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