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Toward Multiple Conductance Pathways with Heterocycle-Based Oligo(phenyleneethynylene) Derivatives

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Departamento de Química Orgánica, Universidad de Granada, C. U. Fuentenueva, Avda. Severo Ochoa s/n, E-18071 Granada, Spain
Fundación IMDEA Nanociencia, Ciudad Universitaria de Cantoblanco, E-28049 Madrid, Spain
§ Departamento of Física Teórica de la Materia Condensada, Universidad Autónoma de Madrid, Ciudad Universitaria de Cantoblanco, E-28049 Madrid, Spain
Nanomaterials Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568, Japan
Departamento de Química Orgánica, Universidad Autónoma de Madrid, Ciudad Universitaria de Cantoblanco, E-28049 Madrid, Spain
# Departamento de Física de la Materia Condensada and Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, E-28049 Madrid, Spain
Instituto “Nicolás Cabrera”, Universidad Autónoma de Madrid, Ciudad Universitaria de Cantoblanco, E-28049 Madrid, Spain
Cite this: J. Am. Chem. Soc. 2015, 137, 43, 13818–13826
Publication Date (Web):October 9, 2015
https://doi.org/10.1021/jacs.5b05637
Copyright © 2015 American Chemical Society
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Abstract

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In this paper, we have systematically studied how the replacement of a benzene ring by a heterocyclic compound in oligo(phenyleneethynylene) (OPE) derivatives affects the conductance of a molecular wire using the scanning tunneling microscope-based break junction technique. We describe for the first time how OPE derivatives with a central pyrimidine ring can efficiently link to the gold electrode by two pathways presenting two different conductance G values. We have demonstrated that this effect is associated with the presence of two efficient conductive pathways of different length: the conventional end-to-end configuration, and another with one of the electrodes linked directly to the central ring. This represents one of the few examples in which two defined conductive states can be set up in a single molecule without the aid of an external stimulus. Moreover, we have observed that the conductance through the full length of the heterocycle-based OPEs is basically unaffected by the presence of the heterocycle. All these results and the simplicity of the proposed molecules push forward the development of compounds with multiple conductance pathways, which would be a breakthrough in the field of molecular electronics.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.5b05637.

  • General procedures for Sonogashira couplings and alternative route for the synthesis of compound 4; copies of 1H NMR and 13C NMR spectra of new compounds 14, 7; copies of elemental analysis, HPLC chromatogram and UV of pyrimidine derivative 4; comparison of the conductance histogram for compound 1 with those for OPE–dithiol and diamine; plateau lengths for all the studied compounds; fits to the plateau length distribution for compounds 1 and 4; examples of individual G vs z traces for compounds 4, 5 and 7; histograms for the separated G vs z traces with only high or low conductance plateaus; 2D histograms of the scaled IV curves for compound 4; table with the percentage of traces with plateaus and plateau length for the study compounds; theoretical details about molecular orbitals in the gas phase, channel decomposition of the transmission and HOMO–LUMO gap corrections (PDF)

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