Author: Liu, Yu-Li; Zhan, Shun-Ze; Sun, Jing-Xuan; Cai, Hong; Yuan, Zhuo-Li; Zhang, Hai-Feng; Li, Mian; Dang, Li; Ni, Shao-Fei; Weng Ng, Seik; Lu, Weigang; Li, Dan

Source: Angewandte Chemie International Edition, 2023, 62, e202306748.

DOI: 10.1002/anie.202306748

Abstract:

Two metallofullerene frameworks (MFFs) constructed from a penta-shell Keplerate cuprofullerene chloride, C₆₀@Cu₂₄@Cl₄₄@Cu₁₂@Cl₁₂, have been successfully prepared via a C₆₀-templated symmetry-driven strategy. The icosahedral cuprofullerene chloride is assembled on a C₆₀ molecule through [h²-(C=C)]-Cu^I and Cu^ICl coordination bonds, resulting in the penta-shell Keplerate with the C₆₀ 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-I and Cl to C₆₀ 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.