Experimental and Theoretical Study of LuNC@C76,82 Revealing a Cage-cluster Selection Rule

Monometallic cyanide clusterfullerenes (CYCFs) with a chemical formula of MNC@C2n represents as a new type of clusterfullerenes discovered in recent years, the encapsulated metal types are still to yttrium and terbium thus far. This makes it unclear the stabilization mechanism of the host fullerene cages upon the variation of internal MNC clusters. Herein, for the first time, four novel Lu-based CYCFs, namely, LuNC@C2v(19138)-C76, LuNC@C2(5)-C82, LuNC@Cs(6)-C82, and LuNC@C2v(9)-C82, have been successfully obtained and characterized using a combination of mass spectrometry, vis-NIR, single-crystal X-ray diffractometry, and cyclic voltammetry. In particular, X-ray results of LuNC@C2v(19138)-C76 and LuNC@C2(5)-C82 unambiguously demonstrated that the internal LuNC unit assumes a nearly linear configuration in the small C76 cage but a confined triangle in the large C82 one, demonstrating the critical role of the cage structure in regulating the cluster configuration. Further theoretical calculations reveal that the linear and triangular configurations of LuNC clusters are governed by the strong and weak Lu-cage coordination interactions in the C2v(19138)-C76 and C2(5)-C82 cages, respectively. In addition, the exact positions of the internal N and C atoms inside the two cages were well defined by combining the crystallographic data with theoretical calculations, showing that the N atom always resides closer to the metal atom to pursue stronger electrostatic interactions.