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Non‐Planar Perylene Bisimide Analogues with Inserted Carbonyl and Methylene Subunits
Author(s) -
Odajima Mai,
Tajima Keita,
Fukui Norihito,
Shinokubo Hiroshi
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202104882
Subject(s) - perylene , photochemistry , chemistry , deprotonation , methylene , dimer , derivative (finance) , intersystem crossing , molecule , excited state , medicinal chemistry , organic chemistry , singlet state , ion , financial economics , economics , physics , nuclear physics
The synthesis and properties of dinaphthotropone bisimide (DNTrBI) and dinaphthocycloheptatriene bisimide (DNCHepBI) are described. Their molecular design is conceptually based on the insertion of a carbon atom into a perylene bisimide (PBI) core. These molecules adopt non‐planar structures due to the presence of a seven‐membered ring. The PBI derivative into which a carbonyl group was inserted (DNTrBI) immediately underwent nonradiative decay and/or intersystem crossing in its excited state. The PBI derivative into which a methylene group was inserted (DNCHepBI) was susceptible to deprotonation on account of the two electron‐withdrawing naphthalene monoimide units. Subsequent aerobic oxidation resulted in the formation of a C−C bond at the central methylene unit, thus affording a σ‐dimer. The formation of this C−C bond is dynamically redox‐active, i.e., electron injection into the σ‐dimer almost quantitatively regenerated the deprotonated DNCHepBI.