Tuning the optical properties of ZnTPP using carbonyl ring fusion

Spectrochim Acta A Mol Biomol Spectrosc. 2009 Nov;74(4):931-5. doi: 10.1016/j.saa.2009.08.040. Epub 2009 Aug 25.

Abstract

Zinc meso-tetraphenylporphyrin (ZnTPP) was modified in such a way to 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 types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Metalloporphyrins / chemistry*
  • Models, Molecular
  • Molecular Structure
  • Quantum Theory
  • Spectrophotometry, Ultraviolet

Substances

  • Metalloporphyrins
  • zinc tetraphenylporphyrin