2,7- and 4,9-Dialkynyldihydropyrene Molecular Switches: Syntheses, Properties, and Charge Transport in Single-Molecule Junctions

Roemer, Max and Gillespie, Angus and Jago, David and Costa-Milan, David and Alqahtani, Jehan and Hurtado-Gallego, Juan and Sadeghi, Hatef and Lambert, Colin J. and Spackman, Peter R. and Sobolev, Alexandre N. and Skelton, Brian W. and Grosjean, Arnaud and Walkey, Mark and Kampmann, Sven and Vezzoli, Andrea and Simpson, Peter V. and Massi, Massimiliano and Planje, Inco and Rubio-Bollinger, Gabino and Agraït, Nicolás and Higgins, Simon J. and Sangtarash, Sara and Piggott, Matthew J. and Nichols, Richard J. and Koutsantonis, George A. (2022) 2,7- and 4,9-Dialkynyldihydropyrene Molecular Switches: Syntheses, Properties, and Charge Transport in Single-Molecule Junctions. Journal of the American Chemical Society, 144 (28). pp. 12698-12714. ISSN 0002-7863

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Abstract

This paper describes the syntheses of several functionalized dihydropyrene (DHP) molecular switches with different substitution patterns. Regioselective nucleophilic alkylation of a 5-substituted dimethyl isophthalate allowed the development of a workable synthetic protocol for the preparation of 2,7-alkyne-functionalized DHPs. Synthesis of DHPs with surface-anchoring groups in the 2,7- and 4,9-positions is described. The molecular structures of several intermediates and DHPs were elucidated by X-ray single-crystal diffraction. Molecular properties and switching capabilities of both types of DHPs were assessed by light irradiation experiments, spectroelectrochemistry, and cyclic voltammetry. Spectroelectrochemistry, in combination with density functional theory (DFT) calculations, shows reversible electrochemical switching from the DHP forms to the cyclophanediene (CPD) forms. Charge-transport behavior was assessed in single-molecule scanning tunneling microscope (STM) break junctions, combined with density functional theory-based quantum transport calculations. All DHPs with surface-contacting groups form stable molecular junctions. Experiments show that the molecular conductance depends on the substitution pattern of the DHP motif. The conductance was found to decrease with increasing applied bias.