Oxidation of Electron Donor-Substituted Verdazyls: Building Blocks for Molecular Switches

Species that can undergo changes in electronic configuration as a result of an external stimulus such as pH or solvent polarity can play an important role in sensors, conducting polymers, and molecular switches. One way to achieve such structures is to couple two redox-active fragments, where the redox activity of one of them is strongly dependent upon environment. We report on two new verdazyls, one subsituted with a di-tert-butyl phenol group and the other with a dimethylaminophenyl group, that have the potential for such behavior upon oxidation. Oxidation of both verdazyls with copper(II) triflate in acetonitrile gives diamagnetic verdazylium ions characterized by NMR and UV-vis spectroscopies. Deprotonation of the phenol-verdazylium results in electron transfer and a switch from a singlet state to a paramagnetic triplet diradical identified by electron spin resonance. The dimethylaminoverdazylium 9 has a diamagnetic ground state, in line with predictions from simple empirical methods and supported by density functional theory calculations. These results indicate that verdazyls may complement nitroxides as spin carriers in the design of organic molecular electronics.