Radical Chemistry from Diazonium-Terminated Surfaces

Active diazonium groups are attached onto surfaces via oxidative grafting of the 4-phenylacetic diazonium salt. The fraction of the anchored aryldiazonium accessible to (electro)­chemical transformation is determined by electrochemical interrogation. Because enough sites are available to react with radical traps, the ability of the aryldiazonium-anchored surfaces to induce radical surface chemistry is tested. Particularly, a new route to grow polymer brushes from surfaces under ATRP conditions is presented. Such an example of a controlled coupling reaction demonstrates how aryldiazoniums, which are irreversible sources of Ar^• radicals, can sustain long-term radical cross-coupling reactions. Such a strategy of generating dormant radical sources from diazonium precursors is fruitful to the simple, versatile, and sustainable chemical decoration of materials