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

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• 作者：Meng-Sheng Liao ; Tapas Kar ; Sergiu M. Gorun ; and Steve Scheiner
• 刊名：Inorganic Chemistry
• 出版年：2004
• 出版时间：November 1, 2004
• 年：2004
• 卷：43
• 期：22
• 页码：7151 - 7161
• 全文大小：168K
• 年卷期：v.43,no.22(November 1, 2004)
• ISSN：1520-510X

文摘

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 groupsalters 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 ligandsleads to an intermediate-spin ground state, while the strong-field ligands make the system diamagnetic. The electronicconfiguration of a ligated iron phthalocyanine is determined mainly by the axial ligand-field strength but can alsobe affected by peripheral substituents. Axial ligands also exert an effect on ionization potentials and electron affinityand can, as observed experimentally, even change the site of oxidation/reduction.