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Bridge-Length-Dependent Intramolecular Charge Transfer in Bis(dianisylamino)-Terminated Oligo(p-phenylene)s
Masashi Uebe1,2, Kensuke Kaneda1, Shinya Fukuzaki1
1Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.
Abstract:
Radical cations of bis(dianisylamino)-terminated oligo(p-phenylene)s (OPPs) with up to five phenyl moieties were characterized by means of UV/Vis-NIR and variable-temperature ESR spectroscopy to investigate the bridge-length-dependence on intramolecular charge/spin self-exchange between two nitrogen redox-active centers. Additionally, a comparative study between bis(dianisylamine)-based mixed-valence (MV) radical cations connected by p-terphenylene and hexa-peri-hexabenzocoronene (HBC) π-bridging units also provided information on the influence of extended π-conjugation over the OPP-bridge due to the planarization between adjacent phenylene units on the strength of electronic coupling. The present study on a homologous series of organic MV systems clarifies the attenuation factor through the OPP-bridge and the linear relationship between the electrochemical potential splitting and the electronic coupling in the region of intermediate-to-weak electronic coupling regime.
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