PROPERTY DEVELOPMENT OF NOVEL ENDOHEDRAL FULLERENES THROUGH SYNTHETIC RESEARCH

我们已经建立了分子外科手术方法来制造内嵌富勒烯，根据传统的物理程序，只能获得微量的富勒烯。本研究的目的是开发这类新型内嵌富勒烯的新性质.采用分子外科手术方法，首次合成了包氢和包氘的内嵌富勒烯H2@C60和D2@C60.制备了一种含钾的内嵌富勒烯K_3/H_2@C_60，并在低于临界温度Tc=19.2K时成为电超导体。这是对于空C60观察到的相同温度，表明在K掺杂条件下，包封的氢和富勒烯笼之间不存在任何电子相互作用。在顺磁性氮氧自由基存在下，测量了H_2和H_2@C_60质子在不同有机溶剂中的自旋-晶格弛豫速率的双分子贡献。 ...更多信息 字典。研究发现，在相同条件下，顺磁体在H2@C60中的弛豫效应比在H2中增强了5倍.研究了C60、H2@C60和D2@C60对单线态分子氧^1O2的猝灭作用，并与溶液中自由H2和D2的猝灭作用进行了比较。发现H2@C60和D2@C60猝灭^1O2的速率常数大于H2和D2猝灭^1O2的速率常数。这表明π共轭的C60笼的存在对于，^1O2猝灭起着重要作用。合成了含He原子和H2分子的开笼富勒烯。笼外质子的^1H NMR化学位移受内部客体物种的影响，因此表明客体物种和开笼富勒烯笼之间存在一些相互作用。合成了一种开笼富勒烯，其13元环孔的边缘取代了硫原子，而硒原子取代了硫原子。的封装和释放的氢分子进行了检查，并发现，这些过程的激活是较小的，表明孔尺寸已被扩大的硒原子的引入。少

We have established the molecular surgical method for the creation of endohedral fullerenes, which were obtained only in minute amounts according to the conventional physical procedures. The present research aims at the development of new properties in this kind of new endohedral fullerenes.1. Endohedral fullerenes encapsulating hydrogen and also deuterium, H2@C60 and D2@C60, were newly synthesized according to the molecular surgical method.2. An endohedral fullerene doped with potassium, K3/H2@C60, was prepared and it was shown to become an electric superconducter below the critical temperature of Tc=19.2K. This is the same temperature observed for empty C60, indicating the absence of any electronic interaction between encapsulated hydrogen and the fullerene cage under the K-doped conditions.3. The bimolecular contribution to the spin-lattice relaxation rate for the protons of H2 and H2@C60 dissolved in various organic solvents was measured in the presence of paramagnetic nitroxide ra … More dicals. It was found that the relaxation effect of the paramagnets is enhanced five-fold in H2@C60 compared to H2 under the same conditions.4. The quenching of singlet molecular oxygen ^1O2 by C60, H2@C60, and D2@C60 was examined and compared with that by free H2 and D2 in solution. The rate constants for quenching of ^1O2 by H2@C60 and D2@C60 were found to be larger than those for the quenching of ^1O2 by H2 and D2. This indicates that the presence of a pi-conjugated C60 cage plays an important role for the, ^1O2 quenching.5. Open-cage fullerenes incorporating a He atom and a H2 molecule were synthesized. The ^1H NMR chemical shift of a proton attached outside the cage is influenced by the inside guest species, thus indicating the presence of some interaction between the guest species and the open-cage fullerene cage.6. An open-cage fullerene having a selenium atom instead of sulfur at the rim of a 13-membered-ring orifice was newly synthesized. The encapsulation and release of a hydrogen molecule were examined, and it was found that activation of these processes is smaller indicating that the orifice size has been enlarged by introduction of the selenium atom. Less