Double protonation of 1,5-bis(triarylaminoethynyl)anthraquinone to form a paramagnetic pentacyclic dipyrylium salt

Koya Prabhakara Rao, Tetsuro Kusamoto, Fumiyuki Toshimitsu, Kiyotaka Inayoshi, Shoko Kume, Ryota Sakamoto, Hiroshi Nishihara

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37 Citations (Scopus)

Abstract

Protonation-induced intramolecular cyclization reactions of new donor (D)-acceptor (A) and D-A-D conjugated molecules 1- triarylaminoethynylanthraquinone (1-AmAq) and 1,5-bis(triarylaminoethynyl) anthraquinone (1,5-Am2Aq), respectively, were achieved. The former undergoes monoprotonation with bis(trifluoromethanesulfone)imide acid (TFSIH) to give pyrylium salt [1-AmPyl]TFSI, whereas the latter undergoes a novel double proton cyclization reaction to yield 1,5-bis(triarylamino)dipyrylium salt [1,5-Am2Pyl2](TFSI)2 with a new pentacyclic backbone. This divalent cationic salt can be reduced to give the neutral species 2,8-bis(triarylamino)benzo[de]isochromeno[1,8-gh]chromene ([1,5-Am 2Pyl2]0), which maintains the planar pentacyclic backbone. The obtained condensed-ring compounds show unique optical, electrochemical, and magnetic properties due to the extremely narrow HOMO-LUMO gap. In particular, the dication [1,5-Am2Pyl2] 2+ shows paramagnetic behavior with two spins centered on two triarylamine moieties through valence tautomerization with the pentacyclic backbone.

Original languageEnglish
Pages (from-to)12472-12479
Number of pages8
JournalJournal of the American Chemical Society
Volume132
Issue number35
DOIs
Publication statusPublished - Sep 8 2010
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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