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Dimensionally oriented redox‐active π‐conjugated systems
Author(s) -
Hirao Toshikazu,
Saito Kaori
Publication year - 2003
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.200351410
Subject(s) - porphyrin , moiety , conjugated system , chemistry , redox , atropisomer , polymer chemistry , dimer , photochemistry , zinc , ligand (biochemistry) , denticity , stereochemistry , polymer , organic chemistry , crystal structure , biochemistry , receptor
Porphyrins bearing the redox‐active phenylenediamine pendant groups are synthesized to afford dimensionally oriented π‐conjugated systems. The structural and electronic characteristics depend on the atropisomers. In the fluorescence emission spectra, the emission from the porphyrin moiety is almost completely quenched. Zinc complexation of the αααα isomers gives the corresponding zinc porphyrins bearing four phenylenediamine strands. Treatment with a bidentate ligand, DABCO, leads to the sandwich dimer complex, in which the porphyrin moieties are surrounded by π‐conjugated pendant groups. p ‐ t ‐Butylcalix[4]arenes bearing four redox‐active phenylenediamine pendant groups on the lower rim are synthesized and characterized both spectroscopically and electrochemically. The interconversion of the oxidation states of the pendant groups is demonstrated both chemically and electrochemically.