Planar Antiaromatic Core-Modified 24π Hexaphyrin(1.0.1.0.1.0) and 32π Octaphyrin(1.0.1.0.1.0.1.0) Bearing Alternate Hybrid Diheterole Units

Jayaprakash Ajay, Sriram Shirisha, Masatoshi Ishida, Kosuke Ito, Shigeki Mori, Hiroyuki Furuta, Sabapathi Gokulnath

Research output: Contribution to journalArticle

Abstract

The Lewis acid catalyzed self-condensation of hybrid diheterole (furan-pyrrole and thiophene-pyrrole) precursors has afforded novel Hückel antiaromatic 24π hexaphyrin(1.0.1.0.1.0) and 32π octaphyrin(1.0.1.0.1.0.1.0) structures without β-annulated bridges. Single-crystal X-ray diffraction analysis of the hybrid porphyrinoids (S 3 N 3 -ox and O 4 N 4 -ox) revealed a nearly planar conformation and the 1 H NMR spectra suggest the presence of paratropic ring currents. These antiaromatic macrocycles show characteristic optical features and underwent reversible two-electron reduction to Hückel aromatic 26π- and 34π-electron species, respectively, as is evident from the results of spectroscopic and theoretical studies (nucleus-independent chemical shift (NICS) and anisotropy of the current-induced density (ACID) calculations). The incorporation of hybrid diheteroles alternately into expanded porphyrin skeletons provides a novel approach to the fine-tuning of the electronic structures of planar antiaromatic macrocycles.

Original languageEnglish
Pages (from-to)2859-2867
Number of pages9
JournalChemistry - A European Journal
Volume25
Issue number11
DOIs
Publication statusPublished - Feb 21 2019

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Bearings (structural)
Pyrroles
Thiophenes
Lewis Acids
Electrons
Porphyrins
Induced currents
Chemical shift
Thiophene
X ray diffraction analysis
Electronic structure
Conformations
Condensation
Anisotropy
Tuning
Nuclear magnetic resonance
Single crystals
Acids

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

Planar Antiaromatic Core-Modified 24π Hexaphyrin(1.0.1.0.1.0) and 32π Octaphyrin(1.0.1.0.1.0.1.0) Bearing Alternate Hybrid Diheterole Units. / Ajay, Jayaprakash; Shirisha, Sriram; Ishida, Masatoshi; Ito, Kosuke; Mori, Shigeki; Furuta, Hiroyuki; Gokulnath, Sabapathi.

In: Chemistry - A European Journal, Vol. 25, No. 11, 21.02.2019, p. 2859-2867.

Research output: Contribution to journalArticle

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