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Volatile and Thermally Stable Polymeric Tin Trifluoroacetates.
Inorganic Chemistry ( IF 4.6 ) Pub Date : 2020-01-09 , DOI: 10.1021/acs.inorgchem.9b01308
Goran Bačić 1 , Conor D Rankine 2 , Jason D Masuda 3 , Derek A Wann 2 , Seán T Barry 1
Affiliation  

Tin trifluoroacetates are effective vapor phase single-source precursors for F-doped SnO2, but their structures have been poorly understood for decades. Here we undertook a comprehensive structural analysis of these compounds in both the solid and gas phases through a combined single-crystal X-ray crystallography, gas phase electron diffraction, and density functional theory investigation. Tin(II) bis(trifluoroacetate) (1) thermally decomposes into a 1:1 mixture of 1 and ditin(II) μ-oxybis(μ-trifluoroacetate) (2) during sublimation, which then polymerize into hexatin(II)-di-μ3-oxyoctakis(μ-trifluoroacetate) (3) upon solidification. Reversible depolymerization occurred readily upon heating, making 3 a useful vapor phase precursor itself. Tin(IV) tetrakis(trifluoroacetate) (5) was also found to be polymeric in the solid state, but it evaporated as a monomer over 130 °C lower than 3. This counterintuitive improvement in volatility by polymerization was possibly due to the large entropy change during sublimation, which offers a strategic new design feature for vapor phase deposition precursors.

中文翻译:

挥发性和热稳定的聚合三氟乙酸锡。

三氟乙酸锡是掺F的SnO2的有效气相单源前体,但数十年来人们对其结构的了解很少。在这里,我们通过组合的单晶X射线晶体学,气相电子衍射和密度泛函理论研究对固相和气相中的这些化合物进行了全面的结构分析。二(三氟乙酸)锡(II)(1)在升华过程中热分解为1和二锡(II)μ-氧基双(μ-三氟乙酸盐)(2)的1:1混合物,然后聚合成六(II)-二固化后的-μ3-氧辛基(μ-三氟乙酸盐)(3)。加热时容易发生可逆解聚,使3本身成为有用的气相前体。还发现四(三氟乙酸)锡(IV)(5)呈固态聚合,
更新日期:2020-01-09
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