The Isomers of Gadolinium Scandium Nitride Clusterfullerenes Gd x Sc 3− x N@C 80 ( x =1, 2) and Their Influence on Cluster Structure

The isomers of gadolinium scandium mixed‐metal nitride clusterfullerenes Gd x Sc 3− x N@C 80 [ x =2 ( 1 , 4 ); x =1 ( 2 , 5 )] have been synthesized by the “reactive gas atmosphere” method and isolated facilely by recycling HPLC. The yield of Gd x Sc 3− x N@C 80 (I, II) ( x =1, 2) relative to the homogenous clusterfullerenes Sc 3 N@C 80 [I ( 3 ), II ( 6 )] was determined. According to the UV/Vis/NIR spectroscopic data, 1 , 2 , 4 , and 5 are all stable fullerenes with large optical gaps. Fullerene 1 has greater similarity to Gd 3 N@C 80 (I) and 2 seems to resemble Sc 3 N@C 80 (I). The quite similar overall absorption features of 4 and 5 suggest pronounced similarity in electronic structure. Vibrational spectroscopic studies led to the assignment of the cage symmetries of Gd x Sc 3− x N@C 80 (I, II), that is, I h for 1 , 2 and D 5 h for 4 , 5 . The cluster–cage interactions in Gd x Sc 3− x N@C 80 (I, II) were analyzed by means of the low‐energy Raman lines. The splitting of the metal–nitrogen stretching vibrational mode in Gd x Sc 3− x N@C 80 (I, II) was studied in detail. Scalar‐relativistic DFT calculations were performed to reveal the geometry parameters and the magnetic state of the Gd x Sc 3− x N@C 80 (I, II) molecules.