Creation of Paramagnetic Endofullerenes by Organic Synthesis

在四（二甲氨基）乙烯存在下，四酮-开笼C60衍生物与元素硫反应，得到在孔缘中含有硫原子的新型开笼C60衍生物和开笼C59S衍生物的第一个实例。单晶X射线分析清楚地确定了这些结构，并证明了水分子被封装在笼内。发现孔尺寸足够大以将N2和O2分子插入分子内。另一方面，我们对He@C60进行了X射线衍射研究，并清楚地观察到C60内部的单个氦原子。此外，氦原子和氮原子在富勒烯内的紧密堆积是使用两种分步插入技术实现的，即，分子手术合成包封氦原子的富勒烯，然后通过氮射频等离子体方法生成包封氦原子和氮原子的富勒烯。

The reaction of a tetraketo-open-cage C60 derivative with elemental sulfur in the presence of tetrakis(dimethylamino)ethylene afforded novel open C60 derivatives containing sulfur atom(s) in the rim of the orifice and the first example of an open C59S derivative. The single crystal X-ray analyses clearly determined these structures and demonstrated that a water molecule was encapsulated inside the cages. The orifice sizes were found to be large enough to insert N2 and O2 molecule inside the molecule. On the other hand, we conducted the X-ray diffraction study of He@C60 and the clear observation of a single helium atom inside C60. In addition, the close packing of a helium atom and a nitrogen atom inside fullerenes is realized using two stepwise insertion techniques, that is, molecular surgery to synthesize the fullerenes encapsulating a helium atom, followed by nitrogen radio-frequency plasma methods to generate the fullerenes encapsulating both helium and nitrogen atoms.