Isolable Bis(triarylamine) Dications_ Analogues of Thiele’s, Chichibabin’s, and Müller’s Hydrocarbons.pdfVIP

Article pubs.acs.org/accounts Isolable Bis(triarylamine) Dications: Analogues of Thiele’s, Chichibabin’s, and Muller’s Hydrocarbons̈ Gengwen Tan and Xinping Wang* State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, China CONSPECTUS: Since the pioneering work by Thiele and Chichibabin, who synthesized the first diradicals bridged by phenylene and biphenylene groups in 1904 and 1907, respec- tively, numerous efforts have been devoted to synthesizing stable diradicals during the last few decades, and several strategies have been developed to stabilize these highly reactive diradicals. In this Account, we describe the synthesis and characterization of iso- lable bis(triarylamine) dications, nitrogen analogues of Thiele’s, Chichibabin’s, and Muller’s hydrocarbons, which represent facilelÿ accessible, stable diradicals by replacing carbinyl centers with isoelectronic aminium centers. Along with discussing the molecular structures and electronic structures of the isolated bis(triarylamine) dications, their spectroscopic and magnetic properties are also introduced. Since 2011, we have reported the stabilization of a variety of radical cations bearing the weakly coordinating anion Al(OR ) − (R = F 4 F polyfluorinated alkyl group), which we have recently successfully applied for the stabilization and crystallization of bis(triarylamine) dications, analogues