Fluoride Ion-Encapsulated Germoxane Cages Modified with Organosiloxane Chains as Anionic Components of Ionic Liquids,Organometallics

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Fluoride Ion-Encapsulated Germoxane Cages Modified with Organosiloxane Chains as Anionic Components of Ionic Liquids
Organometallics ( IF 2.5 ) Pub Date : 2022-05-31 , DOI: 10.1021/acs.organomet.2c00174
Taiki Hayashi ₁ , Nanako Murase ₁ , Naoto Sato ₁ , Koki Fujino ₁ , Natsuhiko Sugimura ₂ , Hiroaki Wada _{1,

3} , Kazuyuki Kuroda _{1,

3} , Atsushi Shimojima _{1,

3}

Affiliation

Herein, we report the preparation of a new class of inorganic–organic hybrid ionic liquids by modification of a double-four-ring (D4R)-type germoxane (Ge–O–Ge) compound, containing a fluoride ion inside and a tetraethylammonium cation outside, with organosiloxane chains. D4R-type inorganic compounds are attractive as anionic components of ionic liquids because of their ability to encapsulate a fluoride ion inside the cage and allow various functional groups to be linked at the cage corners. The crystalline D4R-type germoxanes with corner Ge–OH groups were successfully converted to clear liquids by modification with dimethylvinylsilyl groups, followed by hydrosilylation with flexible oligosiloxanes (HSi(OSiMe₃)_nMe_3–n, n = 1–3). The resulting products showed liquid behaviors below 0 °C and were stable against thermal decomposition up to ∼200 °C. Additionally, they had high affinities for both hydrophilic and hydrophobic substances, attributable to the organosiloxane chains surrounding the ionic cage. Furthermore, the differences between the D4R-type germoxane and D4R-type siloxane were investigated using density functional theory calculations. The symmetry of the optimized structure and its electrostatic nature indicated that D4R-type germoxane is advantageous for the creation of ionic liquids.

中文翻译：

以有机硅氧烷链作为离子液体的阴离子组分改性的氟离子包封锗烷笼

在此，我们报道了通过修饰双四环 (D4R) 型锗氧烷 (Ge-O-Ge) 化合物来制备新型无机-有机杂化离子液体，该化合物内部含有一个氟离子和一个四乙铵阳离子。外面，带有有机硅氧烷链。D4R 型无机化合物作为离子液体的阴离子成分很有吸引力，因为它们能够将氟离子包封在笼内并允许在笼角处连接各种官能团。通过用二甲基乙烯基甲硅烷基改性，然后用柔性低聚硅氧烷 (HSi(OSiMe ₃ ) _n Me _{3– n} , n= 1-3)。所得产物在 0 °C 以下表现出液体行为，并且在高达 200 °C 的温度下对热分解保持稳定。此外，由于离子笼周围的有机硅氧烷链，它们对亲水性和疏水性物质都具有高亲和力。此外，使用密度泛函理论计算研究了 D4R 型锗氧烷和 D4R 型硅氧烷之间的差异。优化结构的对称性及其静电性质表明 D4R 型锗氧烷有利于离子液体的产生。

更新日期：2022-05-31

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