Intervalence transitions in the mixed-valence monocations of bis(triarylamines) linked with vinylene and phenylene-vinylene bridges

Stephen Barlow, Chad Risko, Sung Jae Chung, Neil M. Tucker, Veaceslav Coropceanu, Simon C. Jones, Zerubba Levi, Jean Luc Brédas, Seth R. Marder

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129 Scopus citations


(E)-4,4′-Bis{bis(4-methoxyphenyl)amino}stilbene, 1, (E,E)-1,4-bis[4-{bis(4-methoxyphenyl)-amino}styryl]benzene, 2, and two longer homologues, (E,E,E)-4,4′-bis[4-{bis(4-methoxyphenyl)amino}-styryl] stilbene, 3, and (E,E,E,E)-1,4-bis(4-[4-{bis(4-methoxyphenyl)amino}styryl] styryl)benzene, 4, have been oxidized to their mono- and dications using tris(4-bromophenyl)aminium hexachloroantimonate. The intervalence charge-transfer (IVCT) band of 1+ is narrow and asymmetric and exhibits only weak solvatochromism. Analysis of this band indicates that 1 + is a class-III or class-II/III borderline mixed-valence species. In contrast, a broad, strongly solvatochromic IVCT band is observed for 2 +, indicating that this species is a class-II mixed-valence species. The assignment of 1+ and 2+ as symmetric class-III and unsymmetric class-II species, respectively, is also supported by AM1 calculations. Hush analysis of the IVCT bands of both 1+ and 2 + gives larger electronic couplings, V, than for their analogues in which the double bonds are replaced with triple bonds. The diabatic electron-transfer distance, R, in 1+ can be estimated by comparison of the V estimated by Hush analysis and from the IVCT maximum; it is considerably less than the geometric N-N separation, a result supported by quantum-chemical estimates of R for 1+-4+. In 3 + and 4+, the IVCT is largely obscured by an intense absorption similar to a band seen in the corresponding dications and to that observed in the monocation of a model compound, (E,E,E)-1-{bis(4-methoxyphenyl) amino}-4-[4-{4-(4-tert-butylstyryl)styryl}styryl]benzene, 5, containing only one nitrogen redox center; we attribute this band to a bridge-to-N+ transition. The corresponding dications 12+-42+ show a complementary trend in the coupling between redox centers: the shortest species is diamagnetic, while the dication with the longest bridge behaves as two essentially noninteracting radical centers.

Original languageEnglish
Pages (from-to)16900-16911
Number of pages12
JournalJournal of the American Chemical Society
Issue number48
StatePublished - Dec 7 2005

ASJC Scopus subject areas

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


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