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Effects of Peripheral Substituents on the Electronic Structure and Properties of Unligated and Ligated Metal Phthalocyanines, Metal = Fe, Co, Zn

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    Effects of Peripheral Substituents on the Electronic Structure and Properties of Unligated and Ligated Metal Phthalocyanines, Metal = Fe, Co, Zn
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    Department of Chemistry, P.O. Box 17910, Jackson State University, Jackson, Mississippi 39217, Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey 07102, and Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300
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    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2005, 1, 6, 1201–1210
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    https://doi.org/10.1021/ct050105y
    Published August 27, 2005
    Copyright © 2005 American Chemical Society
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    Abstract

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    The effects of peripheral, multiple −F as well as −C2F5 substituents, on the electronic structure and properties of unligated and ligated metal phthalocyanines, PcM, PcM(acetone)2 (M = Fe, Co, Zn), PcZn(Cl), and PcZn(Cl-), have been investigated using a DFT method. The calculations provide a clear explanation for the changes in the ground state, molecular orbital (MO) energy levels, ionization potentials (IP), electron affinities (EA), charge distribution on the metal (QM), axial binding energies, and in electronic spectra. While the strongly electron-withdrawing −C2F5 groups on the Pc ring change the ground state of PcFe, they do not influence the ground state of PcCo. The IP is increased by ∼1.3 eV from H16PcM to F16PcM and by another ∼1.1 eV from F16PcM to F48PcM. A similar increase in the EA is also found on going from H16PcM to F48PcM. Substitution by the −C2F5 groups also considerably increases the binding strength between PcM and the electron-donating axial ligand(s). Numerous changes in chemical and physical properties observed for the F64PcM compounds can be accounted for by the calculated results.

    Copyright © 2005 American Chemical Society

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    †

     Jackson State University.

    §

     Utah State University.

    *

     Corresponding author e-mail:  [email protected].

    ‡

     New Jersey Institute of Technology.

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    9. Zhenpeng Hu, Bin Li, Aidi Zhao, Jinlong Yang and J. G. Hou. Electronic and Magnetic Properties of Metal Phthalocyanines on Au(111) Surface: A First-Principles Study. The Journal of Physical Chemistry C 2008, 112 (35) , 13650-13655. https://doi.org/10.1021/jp8043048
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    Cite this: J. Chem. Theory Comput. 2005, 1, 6, 1201–1210
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ct050105y
    Published August 27, 2005
    Copyright © 2005 American Chemical Society
    Request reuse permissions

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