Absorption and resonance Raman spectra of Eu sup III (porphyrin) sub 2 sup + complexes. Oxidation-induced enhancement of porphyrin-porphyrin. pi. pi. interaction

Absorption and resonance Raman spectra are reported for the lanthanide porphyrin sandwich complexes Eu{sup III}(OEP){sub 2}{sup +}, Eu{sup III}(TPnP){sub 2}{sup +}, and Eu{sup III}(TPP){sub 2}{sup +} (OEP = octaethylporphyrin, TPnP = meso-tetrapentylporphyrin and TPP = mesotetraphenylporphyrin). The...

Full description

Saved in:
Bibliographic Details
Published inJournal of physical chemistry (1952) Vol. 95:3
Main Authors Perng, Jinghuei, Duchowski, J.K., Bocian, D.F.
Format Journal Article
LanguageEnglish
Published United States 07.02.1991
Subjects
140505 - Solar Energy Conversion- Photochemical, Photobiological, & Thermochemical Conversion- (1980-)
400500 - Photochemistry
ABSORPTION SPECTRA
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
COMPLEXES
EUROPIUM COMPLEXES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MEDIUM TEMPERATURE
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOSYNTHESIS
PHOTOSYNTHETIC REACTION CENTERS
PORPHYRINS
RAMAN SPECTRA
RARE EARTH COMPLEXES
SOLAR ENERGY
SPECTRA
SYNTHESIS
ULTRALOW TEMPERATURE
Online AccessGet full text

Cover

More Information
Summary:Absorption and resonance Raman spectra are reported for the lanthanide porphyrin sandwich complexes Eu{sup III}(OEP){sub 2}{sup +}, Eu{sup III}(TPnP){sub 2}{sup +}, and Eu{sup III}(TPP){sub 2}{sup +} (OEP = octaethylporphyrin, TPnP = meso-tetrapentylporphyrin and TPP = mesotetraphenylporphyrin). These cations contain two holes in the porphyrin {pi} system; consequently, they are electronically similar to solution cation dimers of the form (MOEP{sup +}){sub 2}. All three of the double-hole sandwich complexes exhibit spectral features characteristic of strong {pi}{pi} interactions. In particular, a near-infrared (near-IR)absorption band is observed at 861 nm (Eu{sup III}(OEP){sub 2}{sup +}), 867 nm (Eu{sup III}(TPnP){sub 2}{sup +}), and 1,025 nm (Eu{sup III}(TPP){sub 2}{sup +}). The energies of these near-IR bands are significantly higher than those of the corresponding single-hole complexes. The blue shift of the near-IR absorption maximum of all three double-hole sandwiches undergoes a substantial blue shift as the temperature is lowered from room temperature to 11 K.
ISSN:0022-3654
1541-5740
DOI:10.1021/j100156a053