Synthesis, isolation, spectroscopic and electrochemical characterization of some calcium-containing metallofullerenes

A few Ca-containing mono-metallofullerenes, i.e. Ca@C76, Ca@C88, Ca@C90 (I, II), were synthesized by an improved DC arc discharge method and isolated by a multi-stage HPLC method for the first time. These isomer-separated metallofullerenes were characterized by LD-TOF MS and UV-vis-NIR spectrometry. Their HOMO-LUMO band gaps and possible molecular geometries are discussed according to the absorption spectra in this report. In addition, the cyclic and differential pulse voltammetry of Ca@C76 was conducted in MeCN/C6H5CH3 (1:4 v/v). The voltammograms of Ca@C82 (II, III) and Ca@C84 (II) were also recorded. Their electrochemical behaviors are discussed compared with those of corresponding ytterbium metallofullerenes. The features of the Ca metallofullerenes' electronic structures are also discussed.