Electron spin resonance (ESR) spectroscopy experiments were performed on PPP before electrolysis, after electrolysis, and after preconcentration of the electrolysis product, as shown in Figure . The signals at ~3480 G and ~3650 G indicate the presence of a radical species in the electrolyzed solutions that is not present in the pre-electrolyzed sample. Based on these results, we posit that the high conductance state of PPP arises due to a radical species (Supplementary Figure ), which leads to the formation of a dynamic anchor based on a covalent Au-C linkage (Figure ). Computational modeling including MD simulations and NEGF-DFT calculations was further pursued to complement experimental results.