Structure and bonding properties of the platinum-mediated tetrametallic endohedral fullerene La 3 Pt@C 98 .

Nowadays, focus is on encapsulating a greater variety and amount of metal species into fullerene cages due to their diverse structures and fascinating properties. Nevertheless, the encapsulation of more positively charged metal atoms inside one cage means more Coulomb repulsion, which makes the formation of such endohedral metallofullerenes (EMFs) difficult. In general, non-metallic atoms such as N and O should be introduced as mediators for the formation of trimetallic or tetrametallic endohedral fullerenes. However, it is still unknown whether metal atoms can serve as mediators themselves to form such EMFs. In this paper, the endohedral tetrametallic fullerene La 3 Pt@C 98 with the platinum atom as a metallic mediator is reported. The EMFs of La 3 Pt@C 2 n (2 n = 98-300) were generated by the method of laser ablation in the gas phase and verified by mass spectrometry. Among them, the EMF of La 3 Pt@C 98 was selected and studied by theoretical calculations. Results show that the two most stable isomers are La 3 Pt@ C 2 (231010)-C 98 and La 3 Pt@ C 1 (231005)-C 98 . For both of them, the inner La 3 Pt metallic cluster appears in a pyramidal shape, different from the planar triangular pattern of La 3 N clusters previously reported. Further calculations prove the existence of encaged La-Pt bonds in the La 3 Pt cluster. It was also revealed that the negatively charged Pt atom is situated near the center of the four-center two-electron (4c-2e) metal bond with the highest occupancy number. The platinum-mediated cluster stabilizes the EMFs greatly, promising the possibility of synthesizing new species of Pt-containing EMFs.