Functionalization of nanomaterials with aryldiazonium salts

This paper reviews the surface modification strategies of a wide range of nanomaterials using aryldiazonium salts. After a brief history of diazonium salts since their discovery by Peter Griess in 1858, we will tackle the surface chemistry using these compounds since the first trials in the 1950s. We will then focus on the modern surface chemistry of aryldiazonium salts for the modification of materials, particularly metallic, semiconductors, metal oxide nanoparticles, carbon-based nanostructures, diamond and clays. The successful modification of sp(2) carbon materials and metals by aryldiazonium salts paved the way to innovative strategies for the attachment of aryl layers to metal oxide nanoparticles and nanodiamonds, and intercalation of clays. Interestingly, diazotized surfaces can easily trap nanoparticles and nanotubes while diazotized nanoparticles can be (electro)chemically reduced on electrode/materials surfaces as molecular compounds. Both strategies provided organized 2D surface assembled nanoparticles. In this review, aryldiazonium salts are highlighted as efficient coupling agents for many types of molecular, macromolecular and nanoparticulate species, therefore ensuring stability to colloids on the one hand, and the construction of composite materials and hybrid systems with robust and durable interfaces/interphases, on the other hand. The last section is dedicated to a selection of patents and industrial products based on aryldiazonium-modified nanomaterials. After nearly 160 years of organic chemistry, diazonium salts have entered a new, long and thriving era for the benefit of materials, colloids, and surface scientists. This tempts us to introduce the terminology of "diazonics" we define as the science and technology of aryldiazonium salt-derived materials.