Probing donor-acceptor interactions in meso-substituted Zn(II) porphyrins using resonance raman spectroscopy and computational chemistry

Journal Article


Abstract


  • A series of Zn(II) porphyrins which have asymmetrically substituted meso groups have been studied with UV-vis, resonance Raman, emission spectroscopies, and density functional theory (DFT) calculations. Dye-sensitized solar cells (DSSCs) of these materials have also been fabricated and their performance parameters measured. DFT calculations show perturbation of frontier molecular orbitals, and redox-active substituents cause greater perturbation than nonredox active substituents. All substituents cause a broadening of the B band, as is common for substituted porphyrins. TD-DFT calculations and resonance Raman spectroscopy suggest the donor and acceptor substituents play a small role in transitions of the B band. The meso donor substituent is electronically isolated and does not significantly perturb the molecular orbitals (MOs), while the meso cyanoacrylic acid TiO2 binding group has a much larger effect on the eg MO in particular. However, in the oxidized porphyrin species, the hole is located on the meso substituent, localizing it away from the semiconductor surface, which should reduce recombination and also improve performance. They show modest efficiency when incorporated into solar cells; however, the pattern of behavior is consistent with localization of charge at the meso unit.

Publication Date


  • 2015

Citation


  • van der Salm, H., Lind, S. J., Griffith, M. J., Wagner, P., Wallace, G. G., Officer, D. L. & Gordon, K. C. (2015). Probing donor-acceptor interactions in meso-substituted Zn(II) porphyrins using resonance raman spectroscopy and computational chemistry. The Journal of Physical Chemistry C: Energy Conversion and Storage, Optical and Electronic Devices, Interfaces, Nanomaterials, and Hard Matter, 119 (39), 22379-22391.

Scopus Eid


  • 2-s2.0-84942767059

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/1591

Has Global Citation Frequency


Number Of Pages


  • 12

Start Page


  • 22379

End Page


  • 22391

Volume


  • 119

Issue


  • 39

Place Of Publication


  • United States

Abstract


  • A series of Zn(II) porphyrins which have asymmetrically substituted meso groups have been studied with UV-vis, resonance Raman, emission spectroscopies, and density functional theory (DFT) calculations. Dye-sensitized solar cells (DSSCs) of these materials have also been fabricated and their performance parameters measured. DFT calculations show perturbation of frontier molecular orbitals, and redox-active substituents cause greater perturbation than nonredox active substituents. All substituents cause a broadening of the B band, as is common for substituted porphyrins. TD-DFT calculations and resonance Raman spectroscopy suggest the donor and acceptor substituents play a small role in transitions of the B band. The meso donor substituent is electronically isolated and does not significantly perturb the molecular orbitals (MOs), while the meso cyanoacrylic acid TiO2 binding group has a much larger effect on the eg MO in particular. However, in the oxidized porphyrin species, the hole is located on the meso substituent, localizing it away from the semiconductor surface, which should reduce recombination and also improve performance. They show modest efficiency when incorporated into solar cells; however, the pattern of behavior is consistent with localization of charge at the meso unit.

Publication Date


  • 2015

Citation


  • van der Salm, H., Lind, S. J., Griffith, M. J., Wagner, P., Wallace, G. G., Officer, D. L. & Gordon, K. C. (2015). Probing donor-acceptor interactions in meso-substituted Zn(II) porphyrins using resonance raman spectroscopy and computational chemistry. The Journal of Physical Chemistry C: Energy Conversion and Storage, Optical and Electronic Devices, Interfaces, Nanomaterials, and Hard Matter, 119 (39), 22379-22391.

Scopus Eid


  • 2-s2.0-84942767059

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/1591

Has Global Citation Frequency


Number Of Pages


  • 12

Start Page


  • 22379

End Page


  • 22391

Volume


  • 119

Issue


  • 39

Place Of Publication


  • United States