Self‐Assembly of Nanostructures on Surfaces Using Metal–Organic Coordination

Layer‐by‐layer (LbL) assembly of multilayers is an established method for the construction of layered nanostructures on surfaces, affording control of the thickness, composition, and organization in the vertical direction. Binding between layers is accomplished using various types of interactions, including electrostatic binding, hydrogen bonding, covalent bonding, metal–organic coordination, host–guest interactions, biospecific interactions, and others. Here we focus on LbL assembly using metal–organic coordination, and specifically on layered nanostructures based on bishydroxamate–M 4+ binding. The coordination approach offers attractive features, such as a simple reaction, a defined geometry, and reversibility under certain conditions. The basic scheme includes self‐assembly of a ligand (anchor) monolayer on the surface, followed by alternate binding of metal ions and multi‐functional ligand layers, to form a coordination multilayer. This approach is demonstrated by the construction of a variety of coordinated nanostructures, including bilayers, multilayers, dendrimers, and nanoparticle assemblies, prepared on gold and oxide substrates.