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Aldehyde isomers of porphyrin: A spectroscopic and computational study

Journal Article


Abstract


  • Two diaryl porphyrin isomers have been analyzed using Raman and resonance Raman, electronic absorption,1HNMR spectroscopies coupled with density functional theory approaches. Despite similar nature, these isomers exhibit distinct experimental signatures, which in each case have be simulated by computational methods. Porphyrin saddling may explain the variations seen experimentally, where the degeneration of frontier molecular orbitals occurs. Optical interaction is observed from the aldehyde moiety with contribution to LUMO and LUMO+2 orbitals; and is confirmed by resonance Raman spectroscopy. Configuration interaction is modulated as a function of aldehyde position, resulting in 20% variation of the Q:B ratio from 0.144 to 0.114.

Publication Date


  • 2018

Citation


  • Barnsley, J. E., Wagner, P., Officer, D. L. & Gordon, K. C. (2018). Aldehyde isomers of porphyrin: A spectroscopic and computational study. Journal of Molecular Structure, 1173 665-670.

Scopus Eid


  • 2-s2.0-85053113135

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/3267

Number Of Pages


  • 5

Start Page


  • 665

End Page


  • 670

Volume


  • 1173

Place Of Publication


  • Netherlands

Abstract


  • Two diaryl porphyrin isomers have been analyzed using Raman and resonance Raman, electronic absorption,1HNMR spectroscopies coupled with density functional theory approaches. Despite similar nature, these isomers exhibit distinct experimental signatures, which in each case have be simulated by computational methods. Porphyrin saddling may explain the variations seen experimentally, where the degeneration of frontier molecular orbitals occurs. Optical interaction is observed from the aldehyde moiety with contribution to LUMO and LUMO+2 orbitals; and is confirmed by resonance Raman spectroscopy. Configuration interaction is modulated as a function of aldehyde position, resulting in 20% variation of the Q:B ratio from 0.144 to 0.114.

Publication Date


  • 2018

Citation


  • Barnsley, J. E., Wagner, P., Officer, D. L. & Gordon, K. C. (2018). Aldehyde isomers of porphyrin: A spectroscopic and computational study. Journal of Molecular Structure, 1173 665-670.

Scopus Eid


  • 2-s2.0-85053113135

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/3267

Number Of Pages


  • 5

Start Page


  • 665

End Page


  • 670

Volume


  • 1173

Place Of Publication


  • Netherlands