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Tuning the optical properties of ZnTPP using carbonyl ring fusion

Journal Article


Abstract


  • Zinc meso-tetraphenylporphyrin (ZnTPP) was modified in such awayto allow the effect of an asymmetric

    structural distortion on its optical properties to be investigated. This involved the fusion of a phenyl

    group to an adjacent pyrrole ring via a carbonyl bridge. With the aid of Density Functional Theory (DFT)

    and time-dependent DFT (TD-DFT) calculations it was found that the asymmetric distortion away from

    planarity induced by the carbonyl fusion resulted in a loss of degeneracy in the two lowest unoccupied

    molecular orbitals (LUMOs). The effect was a red shift of the electronic absorbance bands, an increased

    Q:B ratio from 0.046 in ZnTPP to 0.096 in the fused derivative, and the appearance of additional UV–vis

    peaks. This study therefore suggests that structural distortions, as well as electronic substituents may

    be used to alter absorbance spectra, a technique which is of interest in the design of light-harvesting

    dyes.

Publication Date


  • 2009

Citation


  • Cleland, D. M., Gordon, K. C., Wagner, P. W. & Officer, D. L. (2009). Tuning the optical properties of ZnTPP using carbonyl ring fusion. Spectrochimica Acta: Part A Molecular and Biomolecular Spectroscopy, 74 (4), 931-935.

Scopus Eid


  • 2-s2.0-71749083136

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/369

Number Of Pages


  • 4

Start Page


  • 931

End Page


  • 935

Volume


  • 74

Issue


  • 4

Place Of Publication


  • http://www.elsevier.com/locate/saa

Abstract


  • Zinc meso-tetraphenylporphyrin (ZnTPP) was modified in such awayto allow the effect of an asymmetric

    structural distortion on its optical properties to be investigated. This involved the fusion of a phenyl

    group to an adjacent pyrrole ring via a carbonyl bridge. With the aid of Density Functional Theory (DFT)

    and time-dependent DFT (TD-DFT) calculations it was found that the asymmetric distortion away from

    planarity induced by the carbonyl fusion resulted in a loss of degeneracy in the two lowest unoccupied

    molecular orbitals (LUMOs). The effect was a red shift of the electronic absorbance bands, an increased

    Q:B ratio from 0.046 in ZnTPP to 0.096 in the fused derivative, and the appearance of additional UV–vis

    peaks. This study therefore suggests that structural distortions, as well as electronic substituents may

    be used to alter absorbance spectra, a technique which is of interest in the design of light-harvesting

    dyes.

Publication Date


  • 2009

Citation


  • Cleland, D. M., Gordon, K. C., Wagner, P. W. & Officer, D. L. (2009). Tuning the optical properties of ZnTPP using carbonyl ring fusion. Spectrochimica Acta: Part A Molecular and Biomolecular Spectroscopy, 74 (4), 931-935.

Scopus Eid


  • 2-s2.0-71749083136

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/369

Number Of Pages


  • 4

Start Page


  • 931

End Page


  • 935

Volume


  • 74

Issue


  • 4

Place Of Publication


  • http://www.elsevier.com/locate/saa