Abstract
AbstractNature 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.
Highlights
The concept of Supramolecular Electronics arises as a result of blending the studies of organic crystalline systems and the field of conducting polymers.[1]
In the last decade, new crystal structure information on natural biomolecular wires has fascinated the scientific community by revealing the way nature exploits supramolecular electronics using arrays of axially coordinated metalloporphyrins to create highly efficient molecular conduits.[2,3]
Both junctions present multiple conductance features that are attributed to stable pyridine/metalloporphyrin interactions as the STM gap expands giving rise to different supramolecular associations
Summary
The concept of Supramolecular Electronics arises as a result of blending the studies of organic crystalline systems and the field of conducting polymers.[1]. The DPP (metalfree metalloporphyrin) junctions in the presence of both PyrMT and PyrT linkers show both the absence of the highest peak I conductance signature (see SI Section 4.1), which reveals that the peak I feature results from the axial coordination to the metal center in both cases, while peaks II and III are the result of pyridine/porphyrin ring interactions.[19] The final junctions geometries are, unknown.
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