Tuning the Redox Properties of Fullerene Clusters within a Metal–Organic Capsule

A porphyrin-edged metal–organic tetrahedron forms host–guest complexes containing 1–4 equiv of fullerene C60, depending on the solvent employed. The molecules of C60 were bound anticooperatively within well-defined pockets; an X-ray crystal structure of three fullerenes inside the tetrahedron was obtained. Electrochemical measurements revealed that the electron-accepting properties of the fullerenes inside the capsules were altered depending on the mode of encapsulation. The binding of multiple fullerenes was observed to increase the electron affinity of the overall cluster, providing a noncovalent method of tuning fullerene electronics.卟啉封端的金属有机四面体可形成主客体配合物，其中包合的富勒烯C₆₀（fullerene C₆₀）当量数为1~4当量，具体取决于所使用的溶剂。富勒烯C₆₀分子以反协同结合方式锚定在明确界定的空腔内；研究人员获得了该四面体内部包合3个富勒烯的X射线晶体结构。电化学测试表明，胶囊空腔内的富勒烯的电子接受性能会随包封模式的不同而发生改变。当包合多个富勒烯时，整体团簇的电子亲和能会得到提升，这为调控富勒烯的电子特性提供了一种非共价途径。