Unraveling Multi-Anchoring Molecular Junctions via Chemical Surgery

The presence of unintended anchoring sites in functional molecular wires introduces significant complexity into single-molecule conductance measurements, leading to multimodal signals that are challenging to assign. Herein, we introduce a robust analytical framework that synergistically combines statistical histogram analysis with precisely designed molecular editing ("chemical surgery") to resolve this challenge. Using a parent multianchor molecule, we identified its dominant conductance states through cluster analysis of single-molecule conductance data. Subsequently, a series of strategically designed daughter molecules allowed us to surgically dissect the individual contributions of the molecular backbone and each anchoring group. This approach revealed that S-Au binding modes dominate and enabled confident assignment of all the conductance peaks to specific charge pathways. Our work provides a general and powerful strategy for deconvoluting complex conductance data.