meso-Aryl substituted rubyrin and its higher homologues: Structural characterization and chemical properties

Soji Shimizu, Won Seob Cho, Jonathan L. Sessler, Hiroshi Shinokubo, Atsuhiro Osuka

Research output: Contribution to journalArticlepeer-review

42 Citations (Scopus)


meso-Aryl substituted rubyrin ([26]hexaphyrin( 2 and a series of rubyrin-type large expanded porphyrins were obtained from a facile one-pot oxidative coupling reaction of meso-pentafluorophenyl substituted tripyrrane 1. The structures of two of the resulting products were determined by single-crystal X-ray diffraction analysis. Whereas [52]dodecaphyrin-( 4 takes a symmetric helical conformation, the larger species, [62]pentadecaphyrin-( 5, adopts a nonsymmetric distorted conformation in the solid state that contains an intramolecular helical structure. The ability of rubyrin 2 to act as an anion receptor in its diprotonated form (2.2H+) was demonstrated in methanolic solutions. Oxidation of 2 with MnO2 gave [24]rubyrin 6, a species that displays antiaromatic characteristics. [26]Rubyrin 2 and [24]rubyrin 6 both underwent metallation when reacted with Zn-(OAc)2 to give the corresponding biszinc(II) complexes 7 and 8 quantitatively without engendering a change in the oxidation state of the ligands. As a result, complexes 7 and 8 exhibit aromatic and antiaromatic character, respectively. NICS calculation on these compounds also supported aromaticity of 2 and 7, and antiaromaticity of 6 and 8.

Original languageEnglish
Pages (from-to)2668-2678
Number of pages11
JournalChemistry - A European Journal
Issue number9
Publication statusPublished - Mar 17 2008
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry


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