Insertion of transition metal atoms and ions into the nanoscale dodecahedral silsesquioxane (T12-POSS) cage: Structures, stabilities and electronic properties

The geometries of the polyhedral oligomeric silsesquioxane (T12-POSS) cage, (HSiO3/2)12, containing the endohedral transition metal atoms or ions: Sc0,+1,+,2, Ti0,+2, Cr0,+1,+2, Mn0,+1,+2 Fe0,+1,+2, Co0,+1+,2, Ni0,+1,+2, Cu0,+1,+2, Zn0,+1,+2 Mo0 and W0,+1,+2 have been optimized at the B3LYP/6-311G(d,p) level of theory. The density functional theory (DFT) calculations predict that all these transition metal species form endohedral complexes within the T12-POSS cage. The inclusion energies, electronic properties, the HOMO–LUMO gaps, and ionization potentials of these endohedral transition metal T12-POSS complexes and their 31Si and 1H chemical shifts of (SiHO3/2)12 are predicted and discussed.