Building Tailored Interfaces through Covalent Coupling Reactions at Layers Grafted from Aryldiazonium Salts

Aryldiazonium ions are widely used reagents for surface modification. Attractive aspects of their use include wide substrate compatibility (ranging from plastics to carbons to metals and metal oxides), formation of stable covalent bonding to the substrate, simplicity of modification methods that are compatible with organic and aqueous solvents, and the commercial availability of many aniline precursors with a straightforward conversion to the active reagent. Importantly, the strong bonding of the modifying layer to the surface makes the method ideally suited to further on-surface (postfunctionalization) chemistry. After an initial grafting from a suitable aryldiazonium ion to give an anchor layer, a target species can be coupled to the layer, hugely expanding the range of species that can be immobilized. This strategy has been widely employed to prepare materials for numerous applications including chemical sensors, biosensors, catalysis, optoelectronics, composite materials, and energy conversion and storage. In this Review our goal is first to summarize how a target species with a particular functional group may be covalently coupled to an appropriate anchor layer. We then review applications of the resulting materials.