Structure and Properties of Perfluoroalkylated Phthalocyanines: A Theoretical Study

Density functional theory (DFT) calculations are performed on a series of peripherally substituted free-base and fluorinated zinc phthalocyanines, namely F n Pc M (M = 2 H , Zn ; n = 16, 32, 48, 64). F 16 Pc M, F 32 Pc M, and F 48 Pc M all prefer a planar skeletal structure of the metallomacrocycle core. In the case of F 64 Pc , F 64 PcZn remains planar but F 64 PcH 2 is domed. The occurrence of a dome distortion appears to be related, at least in part, to the orientation of the isopropyl - C 3 F 7 substituents as well as to the intermolecular (packing) interactions. The trends in the calculated results of the Pc 2-– M 2+ binding energy, polarizabilities, and electron excitation energies in H 16 Pc M, F 16 Pc M, and F 64 Pc M are in agreement with the experimental observations, as are the geometrical features. It is further confirmed that the simpler F 32 Pc M or F 48 Pc M mimic the basic electronic properties of F64 Pc M .