Variation of counter quaternary ammonium cations of anionic cage germanoxanes as building blocks of nanoporous materials
Variation of counter quaternary ammonium cations of anionic cage germanoxanes as building blocks of nanoporous materials
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DOI：
10.1039/d1dt01122g
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发表时间：
2021-05-07
影响因子：
4
通讯作者：
Kuroda, Kazuyuki
中科院分区：
文献类型：
--
作者：
Hayashi, Taiki;Sato, Naoto;Kuroda, Kazuyuki
双四环（D4R）型笼状锗氧烷在笼中具有氟阴离子，在笼外含有有机铵阳离子作为抗衡阳离子，并且它们作为阴离子多孔材料的独特纳米构建块是有吸引力的。虽然各种抗衡阳离子直接包括在笼锗氧烷合成是有限的，这项研究表明，其他四烷基铵阳离子可以引入离散和交联状态的阳离子交换。在有机溶剂中用四丁基铵（TBA）代替离散笼状锗氧烷的四乙基铵（TEA），这提供了另一种起始材料。将二甲基乙烯基硅烷化笼状锗氧烷与作为连接剂的各种低聚硅氧烷通过硅氢加成反应形成的交联网络中的TEA和TBA阳离子与四甲基铵（TMA）阳离子交换。孔体积的变化，这取决于引入的抗衡阳离子和低聚硅氧烷连接体的类型，进行了验证。在由笼型锗氧烷自下而上合成纳米多孔材料方面，抗衡阳离子和交联剂的选择对于改变孔隙率是重要的。
Double-four ring (D4R)-type cage germanoxanes, having a fluoride anion in the cage, contain organic ammonium cations as counter cations outside the cage, and they are attractive as unique nano-building blocks of anionic porous materials. Although the variety of counter cations directly included in the cage germanoxane synthesis is limited, this study demonstrates that other tetraalkylammonium cations can be introduced by cation exchange in both discrete and cross-linked states. Tetraethylammonium (TEA) of a discrete cage germanoxane was replaced with tetrabutylammonium (TBA) in an organic solvent, which provides another starting material. TEA and TBA cations in cross-linked networks formed by hydrosilylation reactions of dimethylvinylsilylated cage germanoxanes with various oligosiloxanes as linkers were exchanged with tetramethylammonium (TMA) cations. The variation in the pore volume, which depends on the type of introduced counter cations and oligosiloxane linkers, is verified. In terms of bottom-up synthesis of nanoporous materials from cage-type germanoxanes, the selection of both the counter cation and cross-linker is important to vary the porosity.