Crystallographic characterization of Er ₃ N@C _2n (2 n = 80, 82, 84, 88): the importance of a planar Er ₃ N cluster

A series of Er-based nitride clusterfullerenes (NCFs), Er₃N@C_80-88, have been successfully synthesized and isolated. In particular, Er₃N@I_h(7)-C₈₀, Er₃N@D_5h(6)-C₈₀, Er₃N@C_2v(9)-C₈₂, Er₃N@C_s(51365)-C₈₄, and Er₃N@D₂(35)-C₈₈ have been characterized by single-crystal X-ray diffraction (XRD) for the first time. The planar configuration of the inserted Er₃N cluster is identified unambiguously and the Er-N distances increase in accordance with cage expansion to maintain strong metal-cage interactions. Additionally, the electrochemical properties of the Er₃N@C_80-88 series are studied by means of cyclic voltammetry. It is found that the first reduction potentials are roughly similar for all compounds under study, while the first oxidation potentials are cathodically shifted along with the increase of the cage size in the Er₃N@C_2n (2n = 80, 84, 86, 88) series, leading to a decrease in the corresponding electrochemical band gaps. Nevertheless, for Er₃N@C_2v(9)-C₈₂, a good electron donating ability is manifested by its relatively small first oxidation potential, which results from the relatively higher energy level of the highest occupied molecular orbital. The redox behaviors observed in such Er₃N-based NCFs may promise their great potential applications in donor-acceptor systems.