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 language | English (US) |
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Pages (from-to) | 8508-8516 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 127 |
Issue number | 23 |
DOIs | |
State | Published - Jun 15 2005 |
Externally published | Yes |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry
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CCDC 261334: Experimental Crystal Structure Determination
Lambert, C. (Creator), Risko, C. (Creator), Coropceanu, V. (Creator), Schelter, J. (Creator), Amthor, S. (Creator), Gruhn, N. E. (Creator), Durivage, J. C. (Creator) & Brédas, J.-L. (Contributor), Cambridge Crystallographic Data Centre, 2005
DOI: 10.5517/cc8ry42, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc8ry42&sid=DataCite
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