Abstract
Successful isolation and characterization of a series of Er-based dimetallofullerenes present valuable insights into the realm of metal-metal bonding. These species are crystallographically identified as Er2 @Cs (6)-C82 , Er2 @C3v (8)-C82 , Er2 @C1 (12)-C84 , and Er2 @C2v (9)-C86 , in which the structure of the C1 (12)-C84 cage is unambiguously characterized for the first time by single-crystal X-ray diffraction. Interestingly, natural bond orbital analysis demonstrates that the two Er atoms in Er2 @Cs (6)-C82 , Er2 @C3v (8)-C82 , and Er2 @C2v (9)-C86 form a two-electron-two-center Er-Er bond. However, for Er2 @C1 (12)-C84 , with the longest Er⋅⋅⋅Er distance, a one-electron-two-center Er-Er bond may exist. Thus, the difference in the Er⋅⋅⋅Er separation indicates distinct metal bonding natures, suggesting a distance-dependent bonding behavior for the internal dimetallic cluster. Additionally, electrochemical studies suggest that Er2 @C82-86 are good electron donors instead of electron acceptors. Hence, this finding initiates a connection between metal-metal bonding chemistry and fullerene chemistry.
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