Chemical Physics Letters, Vol.467, No.4-6, 348-353, 2009
Insertion of transition metal atoms and ions into the nanoscale dodecahedral silsesquioxane (T-12-POSS) cage: Structures, stabilities and electronic properties
The geometries of the polyhedral oligomeric silsesquioxane (T-12-POSS) cage, (HSiO3/2)(12), containing the endohedral transition metal atoms or ions: Sc-0,Sc-+1,Sc-+,Sc-2, Ti-0,Ti-+2, Cr-0,Cr-+1,Cr-+2, Mn-0,Mn-+1,Mn-+2 Fe-0,Fe-+1,Fe-+2, Co-0,Co-+1+,Co-2, Ni-0,Ni-+1,Ni-+2, Cu-0,Cu-+1,Cu-+2, Zn-0,Zn-+1,Zn-+2 Mo-0 and W-0,W-+1,W-+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 T-12-POSS cage. The inclusion energies, electronic properties, the HOMO-LUMO gaps, and ionization potentials of these endohedral transition metal T-12-POSS complexes and their Si-31 and H-1 chemical shifts of (SiHO3/2)(12) are predicted and discussed. Published by Elsevier B. V.