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Transannular Distance Dependence of Stabilization Energy of the Intramolecular Dimer Radical Cation of Cyclophanes

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journal contribution
posted on 04.05.2006, 00:00 by Mamoru Fujitsuka, Dae Won Cho, Sachiko Tojo, Satoko Yamashiro, Teruo Shinmyozu, Tetsuro Majima
The intramolecular dimer radical cation and charge-transfer complex of various cyclophanes were investigated by using pulse radiolysis measurements. The charge resonance band due to the dimer radical cation of cyclophanes appeared in the near-IR region, which showed a blue-shift as the distance between the two benzene rings of cyclophane decreased. The stabilization energy of the dimer radical cation, which was estimated from the peak position of the charge resonance band, was explained by the exchange interaction, while the substituent effect was small. The absorption peak of the charge-transfer complex with chlorine atom also showed the shift in accordance with the oxidation potential of cyclophanes.