Fluorinated and trifluoromethylated corannulenes

Bernd M. Schmidt, Berit Topolinski, Mihoko Yamada, Shuhei Higashibayashi, Mitsuhiko Shionoya, Hidehiro Sakurai, Dieter Lentz

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

The syntheses and properties of corannulenes carrying electron-withdrawing groups (F, CF3, C6F5) are reported. Direct fluorination of corannulene (C20H10) was carried out with xenon difluoride, and the crystal structure of the product was confirmed by the X-ray analysis. Novel trifluoromethylated corannulenes, including the versatile 4,9-dibromo-1,2-bis(trifluoromethyl)corannulene, were obtained by various established ring-closing reactions. Besides the use of hexafluorobutyne for the construction of fluoranthenes by Diels-Alder reaction as precursor molecules to form 1,2-disubstituted corannulenes, bis(pentafluorophenyl)acetylene was employed as dienophile. The molecular structure and crystal packing of a trifluoromethylated corannulene was determined by single-crystal X-ray analysis and compared with those known brominated and trifluoromethylated corannulenes. The general electron-acceptor properties of corannulenes bearing substituents introduced in particular positions by liquid-phase synthesis are discussed together with published computational results. Stacked bowls: Starting from substituted fluoranthenes, novel corannulenes bearing electron-withdrawing groups were synthesized regioselectively. Moreover, the first fluorinated corannulene was synthesized by direct fluorination. Crystallographically studied trifluoromethylated corannulenes showed desirable π-stacked structures (see figure), despite their electron-acceptor strength in solution.

Original languageEnglish
Pages (from-to)13872-13880
Number of pages9
JournalChemistry - A European Journal
Volume19
Issue number41
DOIs
Publication statusPublished - 2013 Oct 4
Externally publishedYes

Fingerprint

Bearings (structural)
Fluorination
Electrons
X ray analysis
Molecular crystals
Acetylene
Xenon
Molecular structure
Crystal structure
Single crystals
Molecules
corannulene
Liquids

Keywords

  • corannulenes
  • electrochemistry
  • fluorine
  • stacking interactions
  • trifluoromethylation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Schmidt, B. M., Topolinski, B., Yamada, M., Higashibayashi, S., Shionoya, M., Sakurai, H., & Lentz, D. (2013). Fluorinated and trifluoromethylated corannulenes. Chemistry - A European Journal, 19(41), 13872-13880. https://doi.org/10.1002/chem.201301910

Fluorinated and trifluoromethylated corannulenes. / Schmidt, Bernd M.; Topolinski, Berit; Yamada, Mihoko; Higashibayashi, Shuhei; Shionoya, Mitsuhiko; Sakurai, Hidehiro; Lentz, Dieter.

In: Chemistry - A European Journal, Vol. 19, No. 41, 04.10.2013, p. 13872-13880.

Research output: Contribution to journalArticle

Schmidt, BM, Topolinski, B, Yamada, M, Higashibayashi, S, Shionoya, M, Sakurai, H & Lentz, D 2013, 'Fluorinated and trifluoromethylated corannulenes', Chemistry - A European Journal, vol. 19, no. 41, pp. 13872-13880. https://doi.org/10.1002/chem.201301910
Schmidt BM, Topolinski B, Yamada M, Higashibayashi S, Shionoya M, Sakurai H et al. Fluorinated and trifluoromethylated corannulenes. Chemistry - A European Journal. 2013 Oct 4;19(41):13872-13880. https://doi.org/10.1002/chem.201301910
Schmidt, Bernd M. ; Topolinski, Berit ; Yamada, Mihoko ; Higashibayashi, Shuhei ; Shionoya, Mitsuhiko ; Sakurai, Hidehiro ; Lentz, Dieter. / Fluorinated and trifluoromethylated corannulenes. In: Chemistry - A European Journal. 2013 ; Vol. 19, No. 41. pp. 13872-13880.
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