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Published on: April 19, 2019
Radical Cation of Tris(Triarylamine) Connected through 1,2,3-Benzenetriyl Bridge: A Three-Redox-Center Organic
Masashi Uebe1, Koshi Yoshida1, Shu Seki1
1Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.
Abstract:
To explore intramolecular charge-transfer (ICT) pathways in three-redox-center organic mixed-valence (MV) radical cation, a tris(triarylamine) (TTA), in which three triarylamine (TA) redox-active centers are connected in a side-by-side fashion via 1,2,3-benzenetriyl bridging unit, has been newly synthesized. The MV state of the TTA radical cation has been investigated by a combination of experimental and theoretical methods, and the ICT pathway between three redox-active centers has been revealed. The intervalence CT (IVCT) band analysis gave an electronic coupling value comparable to the ortho-phenylene-bridged bis(triarylamine) radical cation. Dynamic electron spin resonance studies clarified that the TTA radical cation was a nondegenerate MV system exhibiting ICT between the central TA and the peripheral TAs through the ortho-phenylene-bridge.
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