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Intramolecular Electron Transfer between Terminal 1,4‐Dimethoxybenzene Units in Radical Cations with a [2.2](1,4)Naphthalenophane, [2.2](1,4)Anthracenophane, and Pentacene Skeleton
Author(s) -
Wartini Alexander R.,
Staab Heinz A.,
Neugebauer Franz A.
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199806)1998:6<1161::aid-ejoc1161>3.0.co;2-1
Subject(s) - chemistry , intramolecular force , unpaired electron , radical ion , delocalized electron , anthracene , photochemistry , pentacene , electron transfer , electron delocalization , stereochemistry , radical , ion , organic chemistry , layer (electronics) , thin film transistor
Various radical cations, in which two terminal 1,4‐dimethoxybenzene units are anellated to [2.2]paracyclophane ( 2b •+ , 3b •+ ), [2.2](1,4)naphthalenophane ( 4d •+ ), and anthracene bridges ( 5 •+ ), have been studied by ESR and ENDOR spectroscopy. In the syn ‐ and anti ‐naphthalenophane radical cations 2b •+ and 3b •+ the delocalization of the unpaired electron over both π‐moieties and the distinct difference between the first and second oxidation potentials, Δ E = E 2 0 – E 1 0 , are evidence for a substantial intramolecular electronic interaction between the two electrophores. Extension of the bridge in 4d •+ and 5 by benzo anellation results in a localized radical cation. Strong intramolecular electronic interaction between the two electrophores is found in the 1,4,8,11‐tetramethoxy‐pentacene radical cation ( 5 •+ ). The syntheses of 4d are described.