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In 2001, ab initio calculations showed that endohedral doping of Zr and Ti atoms leads to extremely steady Zr@Si16 fullerene and Ti@Si16 Frank-Kasper polyhedral groups with big HOMO-LUMO spaces. In 2002, Zr@Ge16 was demonstrated to form a Frank-Kasper polyhedron, recommending the chance of designing book clusters by tuning endohedral and cage atoms. These outcomes had been later confirmed from experiments. In the past almost 2 full decades, numerous