ISSN:
1434-1948
Keywords:
Cerium(IV) bisporphyrinates
;
Sandwich complexes
;
Diporphyrins
;
π Radical-cations and dications
;
Cerium(III) bisporphyrinate anions
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Starting from 5-(4-hydroxyphenyl)-10,15,20-tris(4-methylphenyl)porphyrin (2a), the new bis(porphyrinyloxy)alkanes 4a and 4d were synthesized by ether formation with the α,ω-dibromoalkanes Br(CH2)nBr (n = 8, 11; 3a, 3d). 4a was obtained by a two-step reaction with the 5-[4-(8-bromooctyloxy)phenyl]-10,15,20-tris(4-methylphenyl)porphyrin (2b) as an intermediate. The diporphyrins 4a and 4d were metalated with cerium(III) acetylacetonate to yield the new (porphyrin)cerium sandwich complexes 1a and 1d which were characterized by UV/Vis, IR, 1H-NMR, 13C-NMR spectroscopy and cyclic voltammetry. The mono- and dications and the cerium(III) bisporphyrinate anions of 1a-d were produced by electrochemical oxidation and reduction, respectively, and were examined by UV/Vis/NIR spectroscopy. The length of the lateral chains does not have a specific effect on the first and second oxidation potentials of the porphyrin rings and the reduction potentials of the cerium ions in the bisporphyrinate systems, and on the energy of the NIR bands of the monocations.
Type of Medium:
Electronic Resource
