TY - JOUR
T1 - Tuning Single-Molecule Conductance in Metalloporphyrin-Based Wires via Supramolecular Interactions
AU - Aragonès, Albert C.
AU - Martín-Rodríguez, Alejandro
AU - Aravena, Daniel
AU - Puigmartí-Luis, Josep
AU - Amabilino, David B.
AU - Aliaga-Alcalde, Núria
AU - González-Campo, Arántzazu
AU - Ruiz, Eliseo
AU - Díez-Pérez, Ismael
PY - 2020/1/1
Y1 - 2020/1/1
N2 - 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.
AB - 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.
KW - biomolecular electronics
KW - density functional calculations
KW - metalloporphyrins
KW - single-molecule junctions
KW - supramolecular electronics
UR - http://www.scopus.com/inward/record.url?scp=85089746680&partnerID=8YFLogxK
U2 - 10.1002/ange.202007237
DO - 10.1002/ange.202007237
M3 - Article
SN - 0044-8249
JO - ANGEWANDTE CHEMIE
JF - ANGEWANDTE CHEMIE
ER -