Isolation and crystal structures of two singlet bis(triarylamine) dications with nonquinoidal geometries

Shijun Zheng, Stephen Barlow*, Chad Risko, Tiffany L. Kinnibrugh, Viktor N. Khrustalev, Simon C. Jones, Mikhail Yu Antipin, Neil M. Tucker, Tatiana V. Timofeeva, Veaceslav Coropceanu, Jean Luc Brédas, Seth R. Marder

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

65 Scopus citations


We report the first structural data for bis(diarylamine) "bipolarons": we have isolated and crystallographically characterized salts of the dications obtained by two-electron oxidation of E-4,4′-bis-[di(p-anisyl)amino]stilbene and E,E-2,5-bis{4-[di(p-anisyl) amino]styryl}-3,4-di(n-butoxy)thiophene, [1]2+ and [2]2+ respectively. ESR, NMR, and magnetometry suggest both species have singlet ground states. X-ray structures, together with 1H NMR coupling constants for [2]2+, indicate geometries in which the bond lengths are shifted toward a quinoidal pattern relative to that in the neutral species, but not to a fully quinoidal extent. In particular, the bond-length alternations across the vinylene bridging groups approach zero. DFT calculations with closed-shell singlet configurations reproduce the observed structures well. Our results indicate that singlet species for which one might expect quinoidal geometries (with differences of ca. 0.1 Å between formally single and double bonds) on the basis of a limiting valence-bond representation of the structure can, in fact, show structures with significantly different patterns of bond lengths.

Original languageEnglish (US)
Pages (from-to)1812-1817
Number of pages6
JournalJournal of the American Chemical Society
Issue number6
StatePublished - Feb 15 2006
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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