Peripheral hexabromination, hexaphenylation, and hexaethynylation of meso-aryl-substituted subporphyrins.
Effective peripheral fabrication methods of meso-aryl-substituted subporphyrins were explored for the first time. Hexabrominated subporphyrins 2 were prepared quantitatively from the bromination of subporphyrins 1 with bromine. Hexaphenylated subporphyrins 3 and hexaethynylated subporphyrins 4 and 5 were synthesized by Suzuki-Miyaura coupling and Stille coupling, respectively, in good yields. X-ray crystal structures of 2 b, 3 b, 4 b, and 5 a revealed preservation of the bowl-shaped bent structures with bowl depths similar to that of 1. Hexaethynylated subporphyrins exhibit large two-photon-absorption cross-sections due to effective delocalization of the conjugated network to the ethynyl substituents.
Tsurumaki
Eiji
E
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.
Inokuma
Yasuhide
Y
Easwaramoorthi
Shanmugam
S
Lim
Jong Min
JM
Kim
Dongho
D
Osuka
Atsuhiro
A