Spherical trihedral metallo-borospherenes

The discovery of borospherenes unveiled the capacity of boron to form fullerene-like cage structures. While fullerenes are known to entrap metal atoms to form endohedral metallofullerenes, few metal atoms have been observed to be part of the fullerene cages. Here we report the observation of a class of remarkable metallo-borospherenes, where metal atoms are integral parts of the cage surface. We have produced La 3 B 18 – and Tb 3 B 18 – and probed their structures and bonding using photoelectron spectroscopy and theoretical calculations. Global minimum searches revealed that the most stable structures of Ln 3 B 18 – are hollow cages with D 3 h symmetry. The B 18 -framework in the Ln 3 B 18 – cages can be viewed as consisting of two triangular B 6 motifs connected by three B 2 units, forming three shared B 10 rings which are coordinated to the three Ln atoms on the cage surface. These metallo-borospherenes represent a new class of unusual geometry that has not been observed in chemistry heretofore. Borospherenes are the boron-based analogs of fullerene cages. Here, the authors report a class of Ln 3 B 18 – metallo-borospherenes with unusual spherical trihedron geometry, in which the lanthanide atoms surprisingly form a part of the cage surface.