Sm@C2v(19138)-C76: A Non-IPR Cage Stabilized by a Divalent Metal Ion
1‡Beijing National Laboratory for Molecular Sciences, State Key Lab of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Abstract:
Although a non-IPR fullerene cage is common for endohedral cluster fullerenes, it is very rare for conventional endofullerenes M@C2n, probably because of the minimum geometry fit effect of the endohedral single metal ion. In this work, we report on a new non-IPR endofullerene Sm@C2v(19138)-C76, including its structural and electrochemical features. A combined study of single-crystal X-ray diffraction and DFT calculations not only elucidates the non-IPR cage structure of C2v(19138)-C76 but also suggests that the endohedral Sm(2+) ion prefers to reside along the C2 cage axis and close to the fused pentagon unit in the cage framework, indicative of a significant metal-cage interaction, which alone can stabilize the non-IPR cage. Furthermore, electrochemical studies reveal the fully reversible redox behaviors and small electrochemical gap of Sm@C2v(19138)-C76, which are comparable to those of IPR species Sm@D3h-C74.
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