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Peripheral Hexabromination, Hexaphenylation, and Hexaethynylation of meso ‐Aryl‐Substituted Subporphyrins
Author(s) -
Tsurumaki Eiji,
Inokuma Yasuhide,
Easwaramoorthi Shanmugam,
Lim Jong Min,
Kim Dongho,
Osuka Atsuhiro
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200801802
Subject(s) - bromine , delocalized electron , bent molecular geometry , aryl , conjugated system , stille reaction , chemistry , halogenation , absorption (acoustics) , crystallography , photochemistry , materials science , polymer , organic chemistry , alkyl , composite material
Abstract 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.