Display options
Cite
Lambert C, Risko C, Coropceanu V, et al. Electronic coupling in tetraanisylarylenediamine mixed-valence systems: the interplay between bridge energy and geometric factors. J Am Chem Soc. 2005;127(23):8508-16doi: 10.1021/ja0512172.
Lambert, C., Risko, C., Coropceanu, V., Schelter, J., Amthor, S., Gruhn, N. E., Durivage, J. C., & Brédas, J. L. (2005). Electronic coupling in tetraanisylarylenediamine mixed-valence systems: the interplay between bridge energy and geometric factors. Journal of the American Chemical Society, 127(23), 8508-16. https://doi.org/10.1021/ja0512172
Lambert, Christoph, et al. "Electronic coupling in tetraanisylarylenediamine mixed-valence systems: the interplay between bridge energy and geometric factors." Journal of the American Chemical Society vol. 127,23 (2005): 8508-16. doi: https://doi.org/10.1021/ja0512172
Lambert C, Risko C, Coropceanu V, Schelter J, Amthor S, Gruhn NE, Durivage JC, Brédas JL. Electronic coupling in tetraanisylarylenediamine mixed-valence systems: the interplay between bridge energy and geometric factors. J Am Chem Soc. 2005 Jun 15;127(23):8508-16. doi: 10.1021/ja0512172. PMID: 15941286.
Copy Download .nbib Format: NLM
Share it on

J Am Chem Soc. 2005 Jun 15;127(23):8508-16. doi: 10.1021/ja0512172.

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

Journal of the American Chemical Society

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

Affiliations

  1. Institut für Organische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany. [email protected]

PMID: 15941286 DOI: 10.1021/ja0512172

Abstract

We have investigated three organic mixed-valence systems that possess nearly identical inter-redox 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.

Publication Types