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Asymmetry-Induced Redistribution in Sn(IV)–Ti(IV) Hetero-Bimetallic Alkoxide Precursors and Its Impact on Thin-Film Deposition by Metal–Organic Chemical Vapor Deposition

Abstract : With an aim to enhance the stability and volatility of the heterometallic derivative [SnCl4(µ-OEt)2Ti(OEt)2(HOEt)2] (A), obtained conveniently and quantitatively as a simple adduct formula from the equivalent reaction of commercially available SnCl4 and Ti(OEt)4 in toluene/ethanol, its modification with 2,2,6,6-heptane-3,5-dione (thdH) is reported. The modified precursor [SnCl4(µ-OEt)2Ti(thd)(OEt)(HOEt)] (1), obtained from equimolar reaction of A and thdH, is stable at room temperature but rearranges on heating into A and [SnCl4(µ-OEt)2Ti(thd)2] (2), as confirmed by the vapor pressure measurements and DFT calculations. The heterometallic 2 can be obtained in excellent yield from the reaction of A and thdH in 1:2 molar ratio and is stable in solid and solution phase up to 200 °C. However, the asymmetric nature of its structure consisting of fragments of titanium β-diketonate and tin chloride connected by bridging ethoxo groups, leads to breakdown into two homometallic components in gas phase, leading to deposition of tin-rich metal oxide films on the substrate.
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https://hal.archives-ouvertes.fr/hal-03510420
Contributor : Ioana Nuta Connect in order to contact the contributor
Submitted on : Tuesday, January 4, 2022 - 2:54:09 PM
Last modification on : Monday, February 7, 2022 - 3:06:59 PM

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Shashank Mishra, Erwann Jeanneau, Liang Tian, Ioana Nuta, Elisabeth Blanquet, et al.. Asymmetry-Induced Redistribution in Sn(IV)–Ti(IV) Hetero-Bimetallic Alkoxide Precursors and Its Impact on Thin-Film Deposition by Metal–Organic Chemical Vapor Deposition. Crystal Growth & Design, American Chemical Society, 2021, ⟨10.1021/acs.cgd.1c01136⟩. ⟨hal-03510420⟩

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