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Singly and Doubly 1,2‐Phenylene‐Inserted Porphyrin Arch‐Tape Dimers: Synthesis and Highly Contorted Structures
Author(s) -
Fukui Norihito,
Osuka Atsuhiro
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201802494
Subject(s) - porphyrin , phenylene , crystallography , ring (chemistry) , materials science , homo/lumo , molecular wire , chemistry , photochemistry , molecule , stereochemistry , polymer , organic chemistry
Singly and doubly 1,2‐phenylene‐inserted Ni II porphyrin arch‐tape dimers 3 and 9 were synthesized from the corresponding β‐to‐β 1,2‐phenylene‐bridged Ni II porphyrin dimers 5 and 11 via Ni 0 ‐mediated reductive cyclization and DDQ/Sc(OTf) 3 ‐promoted oxidative cyclization as key steps, respectively. Owing to the fused eight‐membered ring(s), 3 showed a more contorted structure than those of previously reported arch‐tape dimers 2 a and 2 b possessing a fused seven‐membered ring. Furthermore, 9 displayed much larger molecular contortion. As the molecular contortion increases, the Q band of the absorption spectrum becomes more red‐shifted and the electrochemcial HOMO–LUMO gap becomes smaller, reaching at 1294 nm and 0.77 eV in 9 , respectively. The effect of molecular contortion on the electronic properties was studied by means of DFT calculations.