Hole localization or delocalization an optical, Raman, and redox study of lanthanide porphyrin-phthalocyanine sandwich-type heterocomplexes
- CEA-CNRS URA, Gif-sur-Yvette (France)
- Universite Louis-Pasteur, Strasbourg (France)
A systematic electrochemical, redox, optical absorption, and resonance Raman spectroscopic study of 22 gadolinium and cerium double- and triple-decker tetraphenylporphyrin-phthalocyanine (TPP-Pc) complexes is reported. The work is aimed at elucidating the extent of the localization or delocalization among the chromophore ligands in the mixed complexes, where there exists a charge imbalance between the metal centers and the dianion Pc/TPP ligands, as well as in different oxidation states for these types of complexes. For mixed double- and triple-decker complexes, [vert bar]Pc(M)TPP[vert bar] and [vert bar]TPP(M)TPP[vert bar] (where M = Gd[sup III], Ce[sup IV]), in which the metal cannot be oxidized, it appears that the ligand preferentially oxidized is the Pc moiety. This perfentially localized hole in the phthalocyanine results in new near-infrared transitions which show maxima around 1200-1300 nm for the double-decker complexes and shifts to 1800-2300 nm for the triple-decker derivatives. In this case, the removal of an electron from a complex redox orbital which is rich in Pc character is easily identified by the accompanying changes in the optical absorption characteristic of a Pc[sup [sm bullet][minus]] species and is also seen in FT Raman spectra (excited at 1064 nm) by a significant (>15 cm[sup [minus]1]) upshift of a redox-sensitive Raman band at ca. 1500 cm[sup [minus]1]. 33 refs., 13 figs., 2 tabs.
- OSTI ID:
- 6970766
- Journal Information:
- Journal of Physical Chemistry; (United States), Vol. 98:34; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
CERIUM COMPLEXES
ABSORPTION SPECTRA
ELECTROCHEMISTRY
OPTICAL PROPERTIES
RAMAN SPECTROSCOPY
REDOX REACTIONS
GADOLINIUM COMPLEXES
COMPILED DATA
LIGANDS
PHTHALOCYANINES
PORPHYRINS
RADICALS
RARE EARTH COMPLEXES
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DYES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
LASER SPECTROSCOPY
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHYSICAL PROPERTIES
SPECTRA
SPECTROSCOPY
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures
400702 - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials
400400 - Electrochemistry
400500 - Photochemistry