The two-dimensional band structure of (polyphthalocyaninato)Ni(II)

The two-dimensional (2D) band structure of (polyphthalocyaninato)Ni(II), Ni(ppc), has been analyzed by a self-consistent field (SCF ) Hartree–Fock (HF ) crystal orbital (CO ) formalism based on an INDO (intermediate neglect of differential overlap) type Hamiltonian. The calculated HF band gap of Ni(ppc) amounts to 0.24 eV. The highest filled band is a ringlike a_1u combination (D_4h symmetry label) localized at the carbon sites of the organic fragment. Remarkable hybridization in the valence band leads to the considerable band width Δ?_v of 2.92 eV. This value is close to the Δ?_v numbers which are conventionally encountered in one-dimensional metallomacrocycles. The effective width of the states in Ni(ppc) is 13.8 eV. In graphite a net π interval of 13.0 eV is predicted by the present CO formalism; i.e., the energetic distribution of the π electrons is roughly comparable in both 2D solids. The Ni 3d states in Ni(ppc) are far below the Fermi level which is calculated at ?4.9 eV; they are predicted between ?12.2 and ?16.4 eV in the mean-field approximation. Quasi-particle corrections lead to a significant shift of these strongly metal-centered states. Important electronic structure properties of Ni(ppc) are compared with those of 1D metallomacrocycles with similar molecular stoichiometry. The total density of states distribution of Ni(ppc) has been fragmented into projected (ligand π and σ, Ni 3d) contributions in order to allow for a transparent interpretation of the 2D band structure.