Macrocyclic Poly Arylamines for Rigid Connection of Poly Radical Cation Spins

Abstract

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 32+ has dual N and N‘ connection of its p-phenylenediamine radical cation units via 2,7-naphthalene bridges. By ESR and NMR analysis, 32+ 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.