Meso-trifluoromethyl-substituted expanded porphyrins

Soji Shimizu, Naoki Aratani, Atsuhiro Osuka

Research output: Contribution to journalArticle

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Abstract

A series of meso-trifluoromethyl-substituted expanded porphyrins, including N-fused [24]pentaphyrin 3, [28]hexaphyrin 4, [32]heptaphyrin 5, [46]decaphyrin 6, and [56]dodecaphyrin 7, were synthesized by means of an acid-catalyzed one-pot condensation reaction of 2-(2,2,2-trifluoro-1-hydroxyethyl)pyrrole (1) as the first examples bearing meso-alkyl substituents. Besides these products, porphyrin 2 and two calix[5]phyrins 8 and 9 were also obtained. [28]Hexaphyrin 4 was quantitatively oxidized to [26]hexaphyrin 14 with MnO2. These expanded porphyrins have been characterized by mass spectrometry, 1H and 19F NMR spectroscopy, and UV/Vis spectroscopy. The single-crystal structures have been determined for 3, 4, 6, 7, and 14. The N-fused [24]pentaphyrin 3 displays a distorted structure containing a tricyclic fused moiety that is similar to those of mejo-aryl-substituted counterparts, whereas 8 and 9 are indicated to take roughly planar conformations with an inverted pyrrole opposite to the sp3-hybridized meso-carbon atom. Both [28]- and [26]hexaphyrins 4 and 14 have figure-of-eight structures. Solid-state structures of the decaphyrin 6 and dodecaphyrin 7 are remarkable, exhibiting a crescent conformation and an intramolecular two-pitch helical conformation, respectively.

Original languageEnglish
Pages (from-to)4909-4918
Number of pages10
JournalChemistry - A European Journal
Volume12
Issue number18
DOIs
Publication statusPublished - Jun 14 2006
Externally publishedYes

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Porphyrins
Conformations
Pyrroles
Bearings (structural)
Condensation reactions
Ultraviolet spectroscopy
Nuclear magnetic resonance spectroscopy
Mass spectrometry
Carbon
Crystal structure
Single crystals
Atoms
Acids

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

Meso-trifluoromethyl-substituted expanded porphyrins. / Shimizu, Soji; Aratani, Naoki; Osuka, Atsuhiro.

In: Chemistry - A European Journal, Vol. 12, No. 18, 14.06.2006, p. 4909-4918.

Research output: Contribution to journalArticle

Shimizu, Soji ; Aratani, Naoki ; Osuka, Atsuhiro. / Meso-trifluoromethyl-substituted expanded porphyrins. In: Chemistry - A European Journal. 2006 ; Vol. 12, No. 18. pp. 4909-4918.
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