Experimental and Theoretical Study of Electronic Structure of Zinc Phthalocyanines ZnPc and ZnPcF16

The electronic structure of zinc phthalocyanines ZnPc and ZnPcF 16 is studied by X-ray emission and X-ray photoelectron spectroscopy methods. Experimental and theoretical parameters of the energy spectrum are analyzed along with the partial composition of highest occupied molecular orbitals (HOMOs) of the molecules of these compounds. It is shown that the frontier high-energy region of ZnPc HOMOs consists of 2 p π atomic orbitals (AOs) of nitrogens from non-equivalent groups (N α , N β ) and 2 p π orbitals of peripheral carbons (C βγδ ) with the participation of 3 d orbitals of zinc which belong to both π (3 d yz , 3 d z 2) and σ ( 3d xy ) types. It is established that fluorine atoms and the central zinc atom in ZnPcF 16 interact with each other by forming delocalized π orbitals with the participation of carbon p π orbitals belonging to α, β, γ, δ groups as well as nitrogen p π orbitals of α and β groups. The HOMO of ZnPcF 16 consists mainly of 2 p x and 2p y AOs of nitrogen (N α and N β ) and carbon (C β and C γδ ) with a small contribution of the 3 d xz, yz orbital of zinc.