Magic Blue [MB, (p-BrC₆H₄)₃N^•+SbCl₆ ^–]-promoted oxidation of the triphenylamine-dyad mm-1 and subsequent reduction using triethylamine lead to formation of a novel tetraphenylbenzidine derivatives 4, which has a highly planar biphenyl moiety and a high HOMO energy. New insights into the oxidizing ability of SbCl₆ ⁻ derive from MB are also described.

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.