Synthesis, ionisation potentials and electron affinities of hexaazatrinaphthylene derivatives

Stephen Barlow, Qing Zhang, Bilal R. Kaafarani, Chad Risko, Fabrice Amy, Calvin K. Chan, Benoit Domercq, Zoya A. Starikova, M. Yu Antipin, Tatiana V. Timofeeva, Bernard Kippelen, Jean Luc Brédas, Antoine Kahn, Seth R. Marder

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Several hexaazatrinaphthylene derivatives and a tris-(thieno) hexaazatriphenylene derivative have been synthesised by reaction of the appropriate diamines with hexaketocyclohexane. The crystal structure of 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazatrinaphthylene has been determined by X-ray diffraction; this reveals a molecular structure in good agreement with that predicted by density functional theory (DFT) calculations and π-stacking with an average spacing between adjacent molecular planes of 3.18 Å. Solid-state ionisation potentials have been measured by using UV photoelectron spectroscopy and fall in the range of 5.99 to 7.76 eV, whereas solid-state electron affinities, measured using inverse photoelectron spectroscopy, vary in the range -2.65 to -4.59 eV. The most easily reduced example is a tris(thieno)hexaazatriphenylene substituted with bis(trifluoro-methyl)phenyl groups; DFT calculations suggest that the highly exothermic electron affinity is due both to the replacement of the outermost phenylene rings of hexaazatrinaphthylene with thieno groups and to the presence of electron-withdrawing bis(trifluoro-methyl)phenyl groups. The rather exothermic electron affinities, the potential for adopting π-stacked structures and the low intramolecular reorganisation energies obtained by DFT calculations suggest that some of these molecules may be useful electron-transport materials.

Original languageEnglish (US)
Pages (from-to)3537-3547
Number of pages11
JournalChemistry - A European Journal
Issue number12
StatePublished - 2007

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Catalysis
  • Organic Chemistry


  • Electron affinities
  • Electron transport
  • Heterocycles
  • Ionization potentials
  • Pi stacking


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