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2020-07-24

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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/200204

Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions

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https://doi.org/10.1002/anie.202007237

Abstract

Supramolecular wires are created in a confined nanoscale junction by using metalloporphyrin coordination chemistry in a similar fashion to that found in bacteria nanowires. Slight chemical changes in the axial ligands and in the porphyrin ring determine the exact final supramolecular scaffold, which defines the electron pathway along the supramolecular wire. 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.

Subject

Teoria del funcional de densitat, Electrònica molecular, Porfirines

Subject (English)

Density functionals, Molecular electronics, Porphyrins

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Articles publicats en revistes (Ciència dels Materials i Química Física)
Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB))

Citation

ARAGONÈS, Albert C., et al. Tuning Single-Molecule Conductance in Metalloporphyrin-based Wires via Supramolecular Interactions. Angewandte Chemie. 2020. Vol. 59, num. 43, pags. 19193-19201. ISSN 0044-8249. [consulted: 15 of August of 2026]. Available at: https://hdl.handle.net/2445/200204

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