Effects of steric and electronic interactions on. pi. pi. overlap in lanthanide porphyrin sandwich complexes

Journal Article · Thu Aug 23 04:00:00 EDT 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100380a031· OSTI ID:6332777

Perng, Jinghuei; Duchowski, J K; Bocian, D F ^[1]

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1. Carnegie Mellon Univ., Pittsburgh, PA (USA)

Electrochemical, infrared, resonance Raman, and optical absorption data are reported for the lanthanide porphyrin sandwich complexes, Ce{sup IV}(TPP){sub 2}, Ce{sup IV}(TPP){sub 2}{sup +}, Eu{sup III}(TPP){sub 2}, Ce{sup IV}(TPnP){sub 2}, Ce{sup IV}(TPnP){sub 2}{sup +}, and Eu{sup III}(TPnP){sub 2} (TPP = meso-tetraphenylporphyrin; TPnP = meso-tetrapentylporphyrin). The two Eu{sup III} complexes contain a single hole in the porphyrin {pi} system and are electronically similar to the Ce{sup IV} sandwich porphyrin cation radicals. Variable-temperature UV-vis and near-infrared (near-IR) spectra are obtained for all four single-hole sandwiches. At high resolution and/or at low temperatures, well-resolved fine structure is observed on the intradimer charge-transfer bands (ca. 1,300 and 1,100 nm for the TPP and TPnP complexes, respectively). These absorptions are dominated by a single Franck-Condon-active vibration. This vibration is assigned as a mode, Q{sub AB}, which contains a significant amount of multicenter character and modulates inter-ring separation.

• OSTI ID: 6332777
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:17; ISSN JPCHA; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102* -- Chemical & Spectral Procedures
ABSORPTION SPECTRA
BONDING
CARBOXYLIC ACIDS
CERIUM
CHEMISTRY
ELECTROCHEMISTRY
ELEMENTS
EUROPIUM
FABRICATION
FINE STRUCTURE
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFRARED SPECTRA
JOINING
MEDIUM TEMPERATURE
METALS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PORPHYRINS
RAMAN SPECTRA
RARE EARTHS
SPECTRA
SPECTROSCOPY