Electronic spectra of porphyrins in the solid state: Newly observed transitions, collective and structural effects, and protein-mimicking environments

Ronald L. Musselman*, Randy W. Larsen, Brian M Hoffman

*Corresponding author for this work

Research output: Contribution to journalReview article

14 Scopus citations

Abstract

Solid-state porphyrins allow detailed electronic spectroscopy, evaluation of structural effects, and new catalytic environments not possible in solution. A difficulty with studying porphyrins and other highly absorbing species with UV-vis spectroscopy in the solid state is the opacity of the samples. Fortunately, this is in fact a major plus with specular reflectance spectroscopy. This paper reviews several solid-state porphyrin systems having notable delocalized electrons, structural effects on spectra and environments that allow heterogeneous catalysis and protein-mimicking environments, all studied with polarized specular reflectance spectroscopy. The porphyrins include free-base and metalloporphyrins with simple (octaethyl) through complex (tetraaza-tetrabenzo) substituents and ring insertions. Applications include new electronic transition assignments, determination of ring vs. metal conductivity, correlation of ring puckering to red-shifting of Q and Soret transitions, and identifying the presence of and environmental effects on porphyrins in network solids.

Original languageEnglish (US)
Pages (from-to)369-380
Number of pages12
JournalCoordination Chemistry Reviews
Volume257
Issue number2
DOIs
StatePublished - Jan 5 2013

Keywords

  • Electronic spectra
  • One-dimensional conductivity
  • Phthalocyanines
  • Porphyrins
  • Ruffling induced red-shift
  • Solid network encapsulation
  • Solid-state
  • Specular reflectance

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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