MOLART · Surface-Confined Metallosupramolecular Architecture: Towards a Novel Coordination Chemistry for the Design of Functional Nanosystems

The fascinating properties of transition metal complexes intrigued generations of scientists and spurred major technological developments. They are decisive for life processes and catalysis. More recently the pertaining coordination interactions were used to assemble discrete nanostructures and supramolecular networks. Here we aim at a rationale for the design of metallosupramolecular architectures in intimate contact with solid supports. We study and control individual functional molecules and their metal-directed assembly at well-defined surfaces in exquisite detail by molecular-level scanning tunneling microscopy and spectroscopy. The atomistic insight gained into the underlying mechanisms and interactions is used to steer the formation of nano-architectures, whose physicochemical properties are characterized by local and space-averaging techniques. We rationalize the full involvement of the surface atomic lattice in the metal-ligand interactions and coordination spheres using advanced spectroscopic techniques and complementary ab initio theoretical calculations. We engineer nanoporous coordination networks with tailored cavities for patterning purposes, confinement and host-guest systems. We develop new concepts for controled molecular motion in nanoscale coordination environments. We explore the redox chemistry and catalytic activity of the presented coordinatively unsaturated sites to develop novel single-site heterogenous catalysts and potentially biomimetic systems. It is suggested that with the described research a novel heading in coordination chemistry can be explored. The properties of metal centers in unique coordination environments challenge our current understanding, whereas their nanoscale control bears promise for distinct and tunable functionalities.