Synthesis and property of three-dimensional curved heterocyclic π-electron molecules with embedded nitrogen atoms

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Abstract

The synthesis and property of new three-dimensional curved heterocyclic π- electron molecules with embedded nitrogen atoms such as helix-, butterfly-, bowl-, and flake-shaped molecules were investigated. Particularly, novel heterocyclic molecules with an embedded hydrazine structure were focused. Hydrazine-embedded helix-shaped bicarbazole, bidimethylacridine, and biphenothiazine were synthesized by dimerization of the corresponding heterocycles. The hydrazine-embedded helical molecules were found to undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species through the acid-triggered N - N bond cleavage reaction. In the case of bidimethylacridine, the disproportionation reaction is highly reversible through neutralization with NEt3 through back electron transfer and N - N bond formation. Utilizing their reversible redox property, the hydrazine-embedded molecules were applied to cathode active materials of rechargeable lithium organic batteries with excellent performance. Ni-mediated coupling of dibromo-dimethylacridine, phenothiazine, or acridone was found to afford double-butterfly- shaped cyclodimers in high yields. Following N - N bond formation gave hydrazine-embedded butterfly-shaped or planar molecules. The double - butterfly-shaped cyclobiphenothiazine was converted to a cyclodimer of carbazole, [2]cyclo-1,8-carbazolylene, through reductive desulfurization. N - N bond formation of [2] cyclo- 1,8-carbazo-lylene afforded hydrazine-embedded bowl-shaped bicarbazole. The bicarbazole was found to possess bowl and twist structures in the neutral state, a shallow bowl structure in the monocation state, and a planar structure in the dication state by X-ray analysis, 13 C NMR, and DFT calcula¬ tions. Hydrazine-embedded helix-, butterfly-, and bowl-shaped molecules expressed reversible oxidation at a wide range of potentials and red-shift of absorption and fluorescence. The bowl - shaped dimer, a flake-shaped cyclotrimer, a square-shaped cyclotetramer, and a hexagon-shaped cyclohexamer of carbazole were synthesized by Ni-mediated coupling of 1,8-dibromocarbazole, and were named [n]cyclo-1,8-carbazolylenes (n = 3,4,6). A flake-shaped [3]cyclo-4,6-dibenzo-furanylene was also obtained from dibromodibenzofuran. B, P, and Si atoms were introduced to [3]-cyclo-1,8-carbazolylene, giving flake-shaped complexes.

Original languageEnglish
Pages (from-to)1209-1221
Number of pages13
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume77
Issue number12
DOIs
Publication statusPublished - 2019

Keywords

  • Absorption
  • Bowl
  • Butterfly
  • Buttery
  • Curve
  • Disproportionation
  • Double - butterfly
  • Flake
  • Fluorescence
  • Helix
  • Heterocycle
  • Hexagon
  • Hydrazine
  • Redox
  • Square
  • Three-dimension
  • π-electron molecule

ASJC Scopus subject areas

  • Organic Chemistry

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