Electronic coupling in tetraanisylarylenediamine mixed-valence systems: The interplay between bridge energy and geometric factors

Christoph Lambert*, Chad Risko, Veaceslav Coropceanu, Jürgen Schelter, Stephan Amthor, Nadine E. Gruhn, Jason C. Durivage, Jean Luc Brédas

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

96 Scopus citations

Abstract

We have investigated three organic mixed-valence systems that possess nearly identical interredox site distances and differ by the nature of the bridging units benzene, naphthalene, and anthracene: the N,N,N′,N′- tetra(4-methoxyphenyl)-1,4-phenylenene-diamine radical cation (1+), the 1,4-bis(N,N-di(4-methoxyphenyl)-amino)naphthalene radical cation (2 +), and the 9,10-bis(N,N-di(4-methoxyphenyl)amino)anthracene radical cation (3+). The electronic interactions in these systems have been studied by means of gas-phase ultraviolet photoelectron spectroscopy, vis/NIR spectroscopy, and electronic-structure calculations. The experimental and theoretical results concur to indicate that the strength of electronic interaction decreases in the following order of bridging units: benzene > naphthalene > anthracene. This finding contradicts the usual expectation that anthracene is superior to benzene as a driving force for electronic communication. We explain these results in terms of a super-exchange mechanism and its strong dependence on steric interactions.

Original languageEnglish (US)
Pages (from-to)8508-8516
Number of pages9
JournalJournal of the American Chemical Society
Volume127
Issue number23
DOIs
StatePublished - Jun 15 2005
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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