Tuning Single‐Molecule Conductance in Metalloporphyrin‐Based Wires via Supramolecular Interactions

Nature has developed supramolecular constructs to deliver outstanding charge‐transport capabilities using metalloporphyrin‐based supramolecular arrays. Herein we incorporate simple, naturally inspired supramolecular interactions via the axial complexation of metalloporphyrins into the formation of a single‐molecule wire in a nanoscale gap. Small structural changes in the axial coordinating linkers result in dramatic changes in the transport properties of the metalloporphyrin‐based wire. The increased flexibility of a pyridine‐4‐yl‐methanethiol ligand due to an extra methyl group, as compared to a more rigid 4‐pyridinethiol linker, allows the pyridine‐4‐yl‐methanethiol ligand to adopt an unexpected highly conductive stacked structure between the two junction electrodes and the metalloporphyrin ring. DFT calculations reveal a molecular junction structure composed of a shifted stack of the two pyridinic linkers and the metalloporphyrin ring. In contrast, the more rigid 4‐mercaptopyridine ligand presents a more classical lifted octahedral coordination of the metalloporphyrin metal center, leading to a longer electron pathway of lower conductance. This works opens to supramolecular electronics, a concept already exploited in natural organisms.