Synthesis of encapsulating cage and characterisation ofencapsulated species

1. A mixture of silsesquioxanes， HイD2nイエD2（SioイD21. 5イD2）イD2nイエD2 was synthesized by·lled hydrolysis of trichlorosilane。使用高效液相色谱法实现的球-八度胺、-decamer和-十二度胺的笼结构的分离和净化。Lipophilic or hydrophilic substituent groups of several sizes were introduced to afford cage silsesquioxanes of different structure and physicochemical properties. 2.固体中的笼状分子，有机溶剂中的溶液，或吸收的相位被γ射线辐射到氢化原子中。它是氢的有效封闭的必要条件，因为封闭的笼子有一个庞大的终端物质组，而且笼子有一个开放的空间围绕着它们在固态的国家。一种有效地消化氢的替代方法是将笼子转移到一个吸收介质上。大的笼子比八角形大，不能在房间温度下封闭氢。在延长的笼中，液体硝基温度在低温度下被稀释，通过五角大楼环。脂质体Octameric Cage eliminate 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 1 s orbital varied by the cage，and that mixing of 2 p electron into the 1 s is little affected by the size of the cage. 6.分子氧化物从笼子外的角度减少了密封氢的旋转的放松时间。T型D21型D2 is affected more efficiently than T型D22型D2 indicating that rapid molecular motion of trilet oxygen is responsible for the reduction of the relaxation times。

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.