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Computational and Spectroscopic Analysis of β-Indandione Modified Zinc Porphyrins

Journal Article


Abstract


  • Porphyrins have characteristic optical properties which give

    them the potential to be used in a range of applications. In this study, a series

    of β-indandione modified zinc porphyrins, systematically changed in terms of

    linker length and substituent, resulted in absorption spectra that are dramatically

    different than that observed for the parent zinc porphyrin (ZnTXP,

    5,10,15,20-tetrakis(3,5-dimethylphenyl)porphyrinato zinc(II)). These changes

    include strong absorptions at 420, 541, and 681 nm (110.2, 57.5, and

    29.2 mM−1 cm−1

    , respectively) for the most perturbed compound. Computational

    studies were conducted and showed the different optical effects are

    due to a reorganization of molecular orbitals (MOs) away from Gouterman’s

    four-orbital model. The substituent effects alter both unoccupied and occupied

    MOs. An increased length of linker group raised the energy of the HOMO−2

    such that it plays a significant role in the observed transitions. The degenerate

    LUMO (eg) set are split by substitution, and this splitting may be increased by

    use of a propylidenodinitrile group, which shows the lowest-energy transitions and the greatest spectral perturbation from

    the parent zinc porphyrin complex. These data are supported by resonance Raman spectroscopy studies which show distinct

    enhancement of phenyl modes for high-energy transitions and indandione modes for lower-energy transitions.

Publication Date


  • 2018

Citation


  • Mapley, J. I., Wagner, P., Officer, D. L. & Gordon, K. C. (2018). Computational and Spectroscopic Analysis of β-Indandione Modified Zinc Porphyrins. The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 122 (18), 4448-4456.

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/3119

Number Of Pages


  • 8

Start Page


  • 4448

End Page


  • 4456

Volume


  • 122

Issue


  • 18

Place Of Publication


  • United States

Abstract


  • Porphyrins have characteristic optical properties which give

    them the potential to be used in a range of applications. In this study, a series

    of β-indandione modified zinc porphyrins, systematically changed in terms of

    linker length and substituent, resulted in absorption spectra that are dramatically

    different than that observed for the parent zinc porphyrin (ZnTXP,

    5,10,15,20-tetrakis(3,5-dimethylphenyl)porphyrinato zinc(II)). These changes

    include strong absorptions at 420, 541, and 681 nm (110.2, 57.5, and

    29.2 mM−1 cm−1

    , respectively) for the most perturbed compound. Computational

    studies were conducted and showed the different optical effects are

    due to a reorganization of molecular orbitals (MOs) away from Gouterman’s

    four-orbital model. The substituent effects alter both unoccupied and occupied

    MOs. An increased length of linker group raised the energy of the HOMO−2

    such that it plays a significant role in the observed transitions. The degenerate

    LUMO (eg) set are split by substitution, and this splitting may be increased by

    use of a propylidenodinitrile group, which shows the lowest-energy transitions and the greatest spectral perturbation from

    the parent zinc porphyrin complex. These data are supported by resonance Raman spectroscopy studies which show distinct

    enhancement of phenyl modes for high-energy transitions and indandione modes for lower-energy transitions.

Publication Date


  • 2018

Citation


  • Mapley, J. I., Wagner, P., Officer, D. L. & Gordon, K. C. (2018). Computational and Spectroscopic Analysis of β-Indandione Modified Zinc Porphyrins. The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 122 (18), 4448-4456.

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/3119

Number Of Pages


  • 8

Start Page


  • 4448

End Page


  • 4456

Volume


  • 122

Issue


  • 18

Place Of Publication


  • United States