Macrocyclic poly arylamines for rigid connection of poly radical cation spins

[GRAPHICS] The synthesis of macrocyclic arylamines 3 and 4 is reported, These structures yield conformationally rigid polyradical cations for investigation of their electron spin properties, Dication 3(2+) has dual N and N' connection of its p-phenylenediamine radical cation units via 2,7-naphthalene bridges, By ESR and NMR analysis, 3(2+) is found to possess a populated, low-lying triplet excited state, Macrocycle 4 undergoes multielectron oxidation as observed by cyclic voltammetry to yield polycations with more limited kinetic stability.