S,C,C- And O,C,C-Bridged Triarylamines and Their Persistent Radical Cations

Shunpei Kataoka, Shuichi Suzuki, Yoshihito Shiota, Kazunari Yoshizawa, Taisuke Matsumoto, Motoko S. Asano, Toshitada Yoshihara, Chitoshi Kitamura, Shin Ichiro Kato

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7 Citations (Scopus)


This work reports the synthesis, crystal structures, and electronic properties of structurally constrained S,C,C- and O,C,C-bridged triarylamine derivatives and their persistent radical cations. O,C,C-Bridged triphenylamines and a dinaphthylphenylamine were obtained through a straightforward synthetic protocol. Similar to a previously reported S,C,C-bridged triphenylamine, the O,C,C-bridged triarylamines were easily oxidized to afford the corresponding radical cations, which were obtained as hexachloroantimonate salts. X-ray crystallographic analyses showed almost planar structures for these O,C,C-bridged triarylamine radical cations, which represent new members of the family of planar triarylamine radical cations without substituents on the aryl rings. Detailed investigations of the electronic properties of the S,C,C- and O,C,C-bridged triarylamine radical cations demonstrated that the spin and positive charge are sufficiently delocalized over the planar triarylamine scaffolds. The results provide the following insights into the effects of the bridging unit (sulfur vs oxygen) and the dibenzo-annulation on the spin delocalization in the bridged triarylamine radical cations: (1) An effective decrease of the spin density on the nitrogen atom is observed for the sulfur bridge relative to the oxygen bridge; and (2) a moderate decrease of the spin density on the oxygen atom rather than the nitrogen atom is induced by the dibenzo-annulation.

Original languageEnglish
Pages (from-to)12559-12568
Number of pages10
JournalJournal of Organic Chemistry
Issue number18
Publication statusPublished - Sept 17 2021

All Science Journal Classification (ASJC) codes

  • Organic Chemistry


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