Abstract
We demonstrate the successful isolation and unambiguous crystallographic characterization of a series of higher carbide cluster metallofullerenes, presenting new insights into the molecular structures and cluster-cage interactions of endohedral metallofullerenes. They are identified as La2C2@C2(41)-C90, La2C2@D3(85)-C92, La2C2@C1(132)-C94, La2C2@C2(157)-C96, La2C2@C1(175)-C98, La2C2@D5(450)-C100, La2C2@Cs(574)-C102, and La2C2@C2(816)-C104. Our experimental results have confirmed that La2C92-106 tend to form carbide cluster metallofullerenes La2C2@C90-104 instead of the dimetallofullerenes La2@C92-10 6, which is rationalized by considering a synergistic effect of inserting a C2 unit into the fullerene cage to ensure strong metal-cage interactions by partially neutralizing the charges from the metal ions and by fulfilling the coordination requirement of the La3+ ions as much as possible.
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