Suppressing the Conductance of Single-Molecule Junctions Fabricated by sp² C-H Bond Metalation

High-conducting single-molecule junctions have attracted a great deal of attention, but insulating single-molecule junctions, which are critical in molecular circuits, have been less investigated due to the long-standing challenges. Herein, the in situ formation of a Au-C linker via electrical-potential-mediated sp² C-H bond metalation of polyfluoroarenes with the assistance of scanning tunneling microscope-based break junction technique is reported. This metalation process is bias-dependent and occurs with an electropositive electrode, and the formed junction is highly oriented. Surprisingly, these polyfluoroarenes exhibit unexpected low conductance even under short molecular lengths and are superior molecular insulators. Flicker noise analysis and DFT calculations confirm that the insulating properties of polyfluoroarenes are ascribed to their multiple fluorine substituents. Our results pave a way for constructing oriented asymmetric molecular junctions and provide an efficient strategy to suppress the single-molecule conductance, which will aid in the design of molecular insulators and advance the development of self-integrating functional molecular circuits.