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Synthesis of encapsulating cage and characterisation ofencapsulated species

包封笼的合成及包封物质的表征

基本信息

批准号：
08404045
负责人：
MATSUDA Yoshihisa
金额：
$ 23.3万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08404045/
关键词：
Atomic hydrogen Encapsulation Silsesquioxane ESR Relaxation time Electron spin echo シロキサン

项目摘要

1. A mixture of silsesquioxanes, HィイD2nィエD2(SioィイD21.5ィエD2)ィイD2nィエD2 was synthesized by controlled hydrolysis of trichlorosilane. Separation and purification of sphero-octamer, -decamer, and -dodecamer which have cage structure were achieved by using HPLC. Lipophilic or hydrophilic substituent groups of several sizes were introduced to afford cage silsesquioxanes of different structure and physicochemical properties.2. Cage molecules in solid, solution in organic solvent, or adsorbed phase were irradiated with γ-ray to encapsulate the hydrogen atom. It is essential for the efficient encapsulation of hydrogen that the encapsulating cage has bulky terminal substituent groups and that the cage has open space around them in the solid state. An alternative way to encapsulate hydrogen efficiently is to disperse the cages on an adsorbing medium.3. The larger cages than octamer do not encapsulate hydrogen at room temperature. The hydrogen encapsulated in the expanded cages at liquid nitrogen temperature eliminates at low temperature through pentameric ring.4. The lipophilic octameric cage eliminates the encapsulated hydrogen hardly in organic solvents compared to solid state.5. Spin Hamiltonian parameters of hydrogen atoms in several cages indicate that the extent of the 1s orbital varied by the size of the cage and that mixing of 2p electron into the 1s is little affected by the size of the cage.6. Molecular oxygen outside of the cage reduces the relaxation time of the spin of the encapsulated hydrogen. TィイD21ィエD2 is affected more efficiently than TィイD22ィエD2 indicating that rapid molecular motion of triplet oxygen is responsible for the reduction of the relaxation times.

1. 通过三氯硅烷的受控水解合成倍半硅氧烷混合物 HiiD2niiD2(SioiiD21.5iiD2)iiD2niiD2。利用HPLC实现了笼状结构的球八聚体、β十聚体、β十二聚体的分离纯化。引入多种大小的亲脂或亲水取代基，得到不同结构和理化性质的笼状倍半硅氧烷。 2．用γ射线照射固体、有机溶剂溶液或吸附相中的笼状分子以封装氢原子。对于有效封装氢来说，封装笼具有庞大的末端取代基并且笼在固态时在它们周围具有开放空间是至关重要的。另一种有效封装氢气的方法是将笼子分散在吸附介质上。3．比八聚体更大的笼在室温下不封装氢。液氮温度下封闭在膨胀笼内的氢在低温下通过五聚环消除。4．与固态相比，亲脂性八聚笼很难消除有机溶剂中封装的氢。5．几个笼中氢原子的自旋哈密顿参数表明，1s轨道的范围随笼的大小而变化，并且2p电子混合到1s中受笼的大小影响很小。6．笼外的分子氧减少了封装的氢自旋的弛豫时间。 TィイD21ィエD2 比 TィイD22ィエD2 更有效地受到影响，表明三线态氧的快速分子运动是弛豫时间减少的原因。