To further understand the role of terminal anchor groups on the conductance behavior of terphenyl derivatives, we synthesized two amine-terminated terphenyls with different alkyl side chain lengths (R4-N and R6-N) using our automated synthesis method (Fig. ). It is known that SMe and NH2 serve as dative coordination anchors for Au electrodes, yet exhibit different contact resistance, binding behavior, and adsorption free energies in single-molecule experiments. Interestingly, our results show that amine-terminated terphenyls exhibit different concentrationdependent conductance behavior compared to their SMe-terminated counterparts. R4-N does not show a high G state even at relatively high concentrations (10 mM), suggesting a lack of side chain-mediated molecular adsorption for R4-N on electrode surfaces (Fig. ) despite containing identical alkyl chains as R4. We posit that this phenomenon arises from the low adsorption free energy and different binding behavior of NH2 compared to SMe anchors, which in turn inhibits backbone adsorption of R4-N at concentrations up to 10 mM. On the other hand, R6-N shows the emergence of an ultra-high conductance state (10 -2 G0) at 1 mM concentration (Fig. ), which contrasts with the behavior of R6 and R4-N. The ultra-high conductance state of R6-N occurs over small molecular displacements and likely arises due to perpendicular transport via Au-pi-orbital interactions (Fig. ), as reported in prior work. If two terminal amine anchors are involved in surface binding, the probability of junction formation is likely reduced due to an inability of the tip to disrupt molecule-surface binding interactions. Terminal amine anchors only contain a single lone electron pair instead of two lone pairs for SMe anchors, which we speculate may decrease the availability for dative interactions between a lone electron pair and the free orbital on the gold tip. This mechanism of transport is consistent with the conductance pattern of R6-H (containing a single terminal SMe anchor) at 1 mM concentration (Supplementary Fig. ), which exhibits a similar ultra-high conductance state (10 -2 G0) as R6-N.