Endohedral metallofullerenes are capable of holding peculiar metal clusters inside the carbon cage. Additionally, these display many chemical and physical properties originating from the complexation between the metal clusters and carbon cages, which could be acquired for wide applications. In this study, two metallofullerenes (Ce2O@C88 and Ce3N@C88) with an identical large C88-D2(35) cage, and their molecular structures and single-molecule conductance properties were investigated comparatively. Characterizations of UV-vis-NIR absorption spectroscopy, Raman spectroscopy, and DFT calculations were employed to determine the geometries and electronic structures of Ce2O@C88 and Ce3N@C88. These molecules revealed varied energy gaps, structural parameters, vibrational modes, and molecular frontier orbitals. Although the two metallofullerenes have an identical cage isomer of C88-D2(35), their different endohedral clusters can influence their structures and physicochemical properties. Furthermore, the single-molecule conductance properties were measured using the scanning tunneling microscopy break junction technique (STM-BJ). The experimental results revealed that Ce2O@C88 has a higher conductance than Ce3N@C88 and C60. This revealed the cluster-dependent electron transportation as well as the significant research value of metallofullerenes with large carbon cages. These results provide guidance for fabricating single-molecule electronic devices.
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