Synthesis of 2,2,3,3‐Tetraphenyl‐5,5,6,6,7,7,8,8‐octamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane – a Phenyl‐substituted Silicon‐containing Cage

Koichi Sato, Takahiro Sasamori
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Abstract

Molecular cages that contain silicon are highly versatile and stable materials with great potential for various scientific and technological applications due to their ability to form stable three‐dimensional frameworks. The synthesis of 2,2,3,3,5,5,6,6,7,7,8,8‐dodecamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane has already been reported and its modifications at the CH moiety have been demonstrated to afford varied functionality. Here, we present the synthesis and characterization of 2,2,3,3‐tetraphenyl‐5,5,6,6,7,7,8,8‐octamethyl‐2,3,5,6,7,8‐hexasilabicyclo[2.2.2]octane, which is a phenyl‐substituted analogue of such a silicon‐containing cage. The Ph‐substituted Si‐containing cage exhibits a low‐lying LUMO due to the hyper‐conjugation including Si–Si, Si–C σ*‐orbitals, and π(phenyl)‐orbitals, which results in a remarkable bathochromic shift in the UV‐vis absorption spectrum.
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2,2,3,3-Tetraphenyl-5,5,6,6,7,7,8,8-octamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane - a Phenyl-substituted Silicon-containing Cage 的合成
含硅的分子笼由于能够形成稳定的三维框架,因此是用途广泛且非常稳定的材料,在各种科学和技术应用领域具有巨大潜力。2,2,3,3,5,5,6,6,7,7,8,8- 十二甲基-2,3,5,6,7,8-六硅杂双环[2.2.2]辛烷的合成已有报道,其 CH 分子的改性已被证明可提供不同的功能性。在这里,我们介绍了 2,2,3,3- 四苯基-5,5,6,6,7,7,8,8-八甲基-2,3,5,6,7,8-六硅杂双环[2.2.2]辛烷的合成和表征,它是这种含硅笼的苯基取代类似物。由于 S-Si、S-C σ*-轨道和 π(苯基)-轨道的超共轭作用,Ph-取代的含硅笼子显示出低洼的 LUMO,从而导致紫外-可见吸收光谱发生显著的浴色偏移。
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