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Quadruply Twisted Hückel‐Aromatic Dodecaphyrin
Author(s) -
Soya Takanori,
Mori Hirotaka,
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.201811433
Subject(s) - antiaromaticity , metalation , chemistry , dimer , phenylene , molecule , aromaticity , conjugated system , molecular switch , stereochemistry , crystallography , organic chemistry , polymer
Molecular topology of π‐conjugated circuits becomes increasingly important in the chemistry of aromatic and antiaromatic compounds. meso‐Pentafluorophenyl‐substituted 5,35‐(1,4‐phenylene)bridged [56]dodecaphyrin was synthesized by condensation of 1,4‐phenylene‐bridged dicarbinol dimer and 5,10,15‐tris‐(pentafluorophenyl)tetrapyrrane followed by oxidation with DDQ and was oxidized to its [54]‐ and [52]congeners in a stepwise manner. Metalation of the [52]dodecaphyrin with Pd 2 (dba) 3 gave two bis‐Pd II complexes that are isomers of metalation sites: anti and syn with regard to the 1,4‐phenylene bridge. The anti‐isomer was easily oxidized to its N‐fused form, a quadruply twisted non‐aromatic or weakly aromatic macrocycle. On the other hand, the syn‐isomer was revealed to be the first example of Hückel aromatic molecule with a quadruply twisted structure.