An Expanded Family of Dysprosium–Scandium Mixed‐Metal Nitride Clusterfullerenes: The Role of the Lanthanide Metal on the Carbon Cage Size Distribution

A large family of dysprosium–scandium (Dy‐Sc) mixed‐metal nitride clusterfullerenes (MMNCFs), Dy_xSc_3?xN@C_2n (x=1, 2, 2n=68, 70, 76–86) have been successfully synthesized and isolated. Among these, the C₇₀ and C₈₂‐based MMNCFs are two new cages that have never been isolated for MMNCFs. Synthesis of Dy_xSc_3?xN@C_2n was accomplished by the “selective organic solid” route using guanidinium thiocyanate as the nitrogen source, and their isolation was fulfilled by recycling HPLC. UV/Vis‐NIR spectroscopic study indicates that almost all Dy_xSc_3?xN@C_2n MMNCFs are kinetically stable fullerenes with optical band gaps beyond 1 eV. This feature is distinctly different to their counterparts Dy₃N@C_2n (78≤2n≤88), whose for optical band‐gaps are below 1 eV for relatively large cages such as C₈₄ and C₈₆. An FTIR spectroscopic study in combination with DFT calculations enables reasonable assignments of the cage isomeric structures of all isolated Dy_xSc_3?xN@C_2n (x=1, 2, 2n=68, 70, 76–86) MMNCFs. The carbon cage size distribution of Dy_xSc_3?xN@C_2n (2n=68, 70, 76–86) is compared to the reported Dy₃N@C_2n (78≤2n≤8) homogeneous NCF and Dy_xSc_3?xN@C_2n (78≤2n≤88) MMNCF families, revealing that the medium‐sized Dy metal plays a crucial role on the expanded cage size distribution of MMNCFs. As a result, Dy_xSc_3?xN@C_2n MMNCFs are the largest MMNCF family reported to date.