Lu@C82, long overshadowed by Lu2C82, is isolated and structurally identified as Lu³⁺@[C2v(9)-C82]3-. Spectroscopy and DFT show metal–cage electrostatics overriding 6s contraction. An endohedral energy descriptor explains Lu2@C82 formation preference and lanthanide metallofullerene nuclearity, resolving the Lu@C82 valence paradox.
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R. Zhang, P. Yu, M. Li, X. Tan, Z. Hu, W. Shen, L. Bao and X. Lu, Chem. Commun., 2026, Accepted Manuscript , DOI: 10.1039/D5CC07103H
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