ExohedralCupro­fullerene: Sequentially ExpandingMetal Olefin Up to a C60@Cu24 Rhombicuboctahedron

Exohedral cupro­fullerenes with 6-, 12-, or 24-nuclearity were obtained by utilizing fluoro­carboxylic/​dicarboxylic acid under solvo­thermal conditions. The 24-nuclear molecule presents a C60@Cu24 core–shell structure with a rhombi­cuboctahedron Cu24 coated on the C60 core, representing the highest nuclearity in metallo­fullerene. The resultant complexes show an efficient absorption of visible light as opposed to the pristine C60. TD-DFT calculations revealed the charge transfer from Cu­(I) and O atoms to the fullerene moiety dominates the photo­physical process.