title: Effects of peripheral substituents and axial ligands on the electronic structure and properties of iron phthalocyanine.
abstract: The effects of peripheral substituents and axial ligands on the electronic structure and properties of iron phthalocyanine, H(16)PcFe, have been investigated using a DFT method. Substitution by electron-withdrawing fluorinated groups alters the ground state of H(16)PcFe and gives rise to large changes in the ionization potentials and electron affinity. For the six-coordinate adducts with acetone, H(2)O, 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.
authors.affiliation: Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300, USA.
authors.forename: Meng-Sheng
authors.initials: MS
authors.lastname: Liao
authors.forename: Tapas
authors.initials: T
authors.lastname: Kar
authors.forename: Sergiu M
authors.initials: SM
authors.lastname: Gorun
authors.forename: Steve
authors.initials: S
authors.lastname: Scheiner
mesh_terms: D000465:Algorithms; D004563:Electrochemistry; D005296:Ferrous Compounds / Q000737:chemistry*; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D007211:Indoles / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D005296:Ferrous Compounds; D006845:Hydrocarbons, Fluorinated; D007211:Indoles; D008024:Ligands; C493990:iron phthalocyanine