Synthesis and Characterization of Some Three Dimensional Cyclic Organosilanes

一些三维环状有机硅烷的合成与表征

基本信息

批准号：
11640527
负责人：
NAKADAIRA Yasuhiro
金额：
$ 1.47万
依托单位：
The University of Electro-Communications
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640527/
关键词：
polysilaxane porous silicon caged organosilane caged siloxane emission fluorescence かご型ポリシロキサン

项目摘要

The emission from the porous silicon has not fully explained yet. Here, in order to take one of possible chemical approaches to clarify the essential structure of the emission of this kind, we have planned to synthesize and characterize some caged solid organosilanes having both silicon-silicon and silicon-oxygen-silicon bonds. Tow types of tetrameric caged polysiloxanes containing silicon-silicon bonds have been prepared by condensation of 1,2- dimethyl-1,1,2,2-tetraethoxy disilane under acidic conditions. They show UV absorption maxima at 235 and 229 nm, respectively. At the same time, they emit as expected at 360 and 351 nm with quantum yields of 0.13 and O.11 respectively. These emissive properties are comp ared with those of two-dimensional analogues and this indicates that such a rigid three-dimensional structure having both silicon-silicon and silicon-oxy gen-silicon bonds should be essential for the efficient emission observed. Then, to examine the substituent effect on the emission, we have prepared the same types of caged polysiloxane with isopropyl groups instead of methyl groups by condensation of 1,2-diisopropyl-1,1,2,2- tetraethoxy disilane under similar acidic conditions. They show UV absorptions at longer wavelength, 256 and 242 nm, respectively, and give the emission maxima at 361 and 350 nm, respectively, with poor quantum efficiency, namely, 0.067 and 0.034, respectively. Phenyl derivatives have been also prepared starting from hydrolysis of 1,2-diphenyl-1,1,2,2- tetrachlorodisilane in aqueous acetone.

多孔硅的排放尚未完全解释。在这里，为了采用一种可能的化学方法来阐明这种排放的基本结构，我们计划合成和表征一些具有硅 - 硅和硅 - 氧气 - 硅质键的笼中的固体有机硅。通过在酸性条件下的1,2-二甲基-1,1,2,2-2-2-2-2-二甲氧甲氧基二硅烷的凝结制备了含有硅 - 硅键的四聚笼多硅氧烷的TOW类型。它们分别显示235 nm和229 nm的紫外吸收最大值。同时，它们按预期在360和351 nm处发射，量子产率分别为0.13和O.11。这些发射特性与二维类似物的特性相结合，这表明具有硅硅硅和硅氧化基因硅键的这种刚性的三维结构对于观察到的有效排放至关重要。然后，为了检查对发射的取代基作用，我们通过在相似的酸性条件下的1,2-二异丙基-1,1,2-2-2-2-2-2-2-2-2-2-四乙氧基二硅烷凝结，制备了与异丙基基团而不是甲基的相同类型的笼中的多硅氧烷。它们分别在较长波长，256和242 nm处显示紫外吸收，分别分别给出361和350 nm的发射最大值，量子效率较差，即0.067和0.034。还从1,2-二苯基-1,1,2,2-四氯二硅烷水解中的水解开始制备了苯基衍生物。