Dioxadiazuliporphyrin: a near-IR redox switchable chromophore

J Org Chem. 2007 Dec 7;72(25):9501-9. doi: 10.1021/jo7015218. Epub 2007 Nov 15.

Abstract

The synthesis of dioxadiazuliporphyrinogen 7 and its oxidized forms: dioxadiazuliporphyrin 8 and dication 8(2+), is reported. These compounds were characterized in solution using UV-vis and 1H and 13C NMR spectroscopic means and in the solid state via single-crystal X-ray diffraction analysis. Dioxadiazuliporphyrin is a nonaromatic porphyrinoid, readily and reversibly oxidizable to its cation radical and to the aromatic carbaporphyrinoid dication, which can be viewed as a 21,23-dicarba-22,24-dioxaporphyrin with two fused tropylium rings. Further insight into the geometric and magnetic manifestations of aromaticity and antiaromaticity in the case of the redox couple 8, 8(2+) is obtained using density functional calculations and nucleus-independent chemical shifts.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Infrared Rays*
  • Magnetic Resonance Spectroscopy / methods
  • Magnetic Resonance Spectroscopy / standards
  • Models, Chemical
  • Models, Molecular
  • Molecular Structure
  • Oxidation-Reduction
  • Porphyrinogens / chemical synthesis
  • Porphyrinogens / chemistry
  • Porphyrinogens / radiation effects
  • Porphyrins / chemical synthesis*
  • Porphyrins / chemistry
  • Porphyrins / radiation effects*
  • Reference Standards
  • Stereoisomerism

Substances

  • Porphyrinogens
  • Porphyrins
  • dioxadiazuliporphyrin
  • dioxadiazuliporphyrinogen