Modeling of the molecular and electronic structures of multiple-decker sandwich macromolecules with η5-π bonds on the basis of biscyclopentadienyl derivatives 60H10 of a C60 fullerene

Abstract

The molecular and electronic structures of the (CpFe)2C60H10 complex of the D5d symmetry, where Cp is the \(^ \cdot C_5 H_5 \) cyclopentadienyl radical, are simulated using the ab initio Hartree-Fock-Roothaan method in the 3–21G basis set. In this complex, hydrogen atoms are attached to carbon atoms of the C60 fullerene which occupy α-positions with respect to two oppositely lying five-membered rings. Each FeCp semisandwich moiety is linked to atoms of one of these five-membered rings by the η5-π-type bond. It is found that the energy of the η5-π Fe-C60H10 bonds in the (CpFe)2C60H10 complex is comparable to that of the η5-π Fe-Cp bond in the FeCp2 ferrocene molecule. The optimum geometry calculated for the (CpFe)2C60H10 complex is used for modeling of the structure of the quasi-linear macromolecule [-FeC60H10-]n, Open image in new window (I). The band structure of the energy spectrum of macromolecule I is calculated in the valence approximation of the extended Huckel method within the crystalline-orbital approach. The band gap in the spectrum of macromolecule I is ∼2.27 eV. The band structure of the spectrum of this macromolecule is compared with the spectra of the hypothetical molecules [-FeCp-]n and [-FeC20-]n.