Effects of Peripheral Substituents and Axial Ligands on the Electronic Structure and Properties of Iron Phthalocyanine

Authors

Meng-Sheng Liao, Utah State University
Tapas Kar, Utah State UniversityFollow
Steve Scheiner, Utah State UniversityFollow

Document Type

Article

Publication Date

2004

Volume

43

Abstract

The effects of peripheral substituents and axial ligands on the electronic structure and properties of iron phthalocyanine, H₁₆PcFe, have been investigated using a DFT method. Substitution by electron-withdrawing fluorinated groups alters the ground state of H₁₆PcFe and gives rise to large changes in the ionization potentials and electron affinity. For the six-coordinate adducts with acetone, H₂O, and pyridine, the axial coordination of two weak-field ligands leads to an intermediate-spin ground state, while the strong-field ligands make the system diamagnetic. The electronic configuration of a ligated iron phthalocyanine is determined mainly by the axial ligand-field strength but can also be affected by peripheral substituents. Axial ligands also exert an effect on ionization potentials and electron affinity and can, as observed experimentally, even change the site of oxidation/reduction.

Recommended Citation

Effects of Peripheral Substituents and Axial Ligands on the Electronic Structure and Properties of Iron Phthalocyanine M.-S. Liao, T. Kar, S. M. Gorun, S. Scheiner Inorg. Chem. 2004 43 7151-7161