Symmetry-Driven Assembly of a Penta-Shell Keplerate Cuprofullerene for Metallofullerene Frameworks.

Two metallofullerene frameworks (MFFs) constructed from a penta-shell Keplerate cuprofullerene chloride, C @Cu @Cl @Cu @Cl , have been successfully prepared via a C -templated symmetry-driven strategy. The icosahedral cuprofullerene chloride is assembled on a C molecule through [η -(C=C)]-Cu and Cu -Cl coordination bonds, resulting in the penta-shell Keplerate with the C core canopied by 24 Cu, 44 Cl, 12 Cu and 12 Cl atoms that fulfill the tic@rco@oae@ico@ico penta-shell polyhedral configuration. By sharing the outmost-shell Cl atoms, the cuprofullerene chlorides are connected into 2D or 3D (snf net) frameworks. TD-DFT calculations reveal that the charge transfer from the outmost Cu and Cl to C core is responsible for their light absorption expansion to near-infrared region, implying anionic halogenation may be an effective strategy to tune the light absorption properties of metallofullerene materials.