Institute for Chemical Research, Kyoto University, Uji, Kyoto, 611-0011, Japan.
Graduate School of Human and Environmental Sciences, Kyoto University, Kyoto, 606-8501, Japan.
Angew Chem Int Ed Engl. 2017 Apr 3;56(15):4261-4265. doi: 10.1002/anie.201701212. Epub 2017 Mar 16.
A supramolecular complex was constructed by encapsulation of a O molecule inside an open-cage C derivative. Its single-crystal X-ray diffraction analysis revealed the presence of the O at the center of the fullerene cage. The CV measurements suggested that unprecedented dehydrogenation was promoted by the encapsulated O after two-electron reduction. The ESR measurements displayed the triplet character as well as the anisotropy of the O . Additionally, the SQUID measurements also demonstrated the paramagnetic behavior above 3 K without an antiferromagnetic transition. Upon photoirradiation with visible light, three phosphorescent bands at the NIR region were observed, arising from the exited O generated by self-sensitization with the outer cage, whose lifetimes were not affected by the environments. These studies confirmed that the complex is a crystalline triplet system with incompatible "high spin density" but "small interspin interaction" properties.
一个超分子复合物是通过将一个 O 分子封装在一个开笼 C 衍生物内部构建的。其单晶 X 射线衍射分析表明，O 分子位于富勒烯笼的中心。CV 测量表明，在双电子还原后，封装的 O 促进了前所未有的脱氢反应。ESR 测量显示了三重态特征以及 O 的各向异性。此外，SQUID 测量也表明在 3 K 以上具有顺磁行为，没有反铁磁转变。可见光光照射后，在近红外区域观察到三个磷光带，源于通过与外笼的自敏化生成的激发态 O，其寿命不受环境影响。这些研究证实，该配合物是具有不兼容“高自旋密度”但“小自旋间相互作用”特性的晶体三重态体系。
