Magic Blue-Promoted Synthesis of a Highly Planar Tetraphenylbenzidine: Evaluation of Its Fundamental Properties and Unraveling the Intriguing Mechanism for Its Formation

Abstract

Magic blue [MB, (p-BrC₆H₄)₃N^•+SbCl₆⁻]-promoted oxidation of the tetracyclodecane derivative mm-1 containing two triphenylamine (TPA) moieties and subsequent reduction using triethylamine results in formation of the uncharged pentacyclic product 4 that possesses a novel, cage-framework-constrained tetraphenylbenzidine (TPB) moiety. This process follows an electron-transfer mechanism involving formation of the intermediate radical cation 4^•+ through intramolecular aryl coupling of a di(radical cation) mm-1^2(•+). The TPB biphenyl type conjugated moiety in 4 is highly planar. Moreover, 4 has a higher energy HOMO and greater electrochemical stability than does the parent TPB. Notably, because it undergoes a fully reversible two-step–two-electron oxidation–reduction reaction, 4 is an ideal electron donor for use in electronic devices. Finally, conversion of 4^•+ to the corresponding dication 4²⁺ by SbCl₆^–-promoted “auto”oxidation is described.