Hopping Conductance in Molecular Wires Exhibits a Large Heavy-Atom Kinetic Isotope Effect

We report a large kinetic isotope effect (KIE) for intramolecular charge transport in π-conjugated oligophenyleneimine (OPI) molecules connected to Au electrodes. ¹³C and ¹⁵N substitution on the imine bonds produces a conductance KIE of ∼2.7 per labeled atom in long OPI wires >4 nm in length, far larger than typical heavy-atom KIEs for chemical reactions. In contrast, isotopic labeling in shorter OPI wires <4 nm does not produce a conductance KIE, consistent with a direct tunneling mechanism. Temperature-dependent measurements reveal that conductance for a long ¹⁵N-substituted OPI wire is activated, and we propose that the exceptionally large conductance KIEs imply a thermally assisted, through-barrier polaron tunneling mechanism. In general, observation of large conductance KIEs opens up considerable opportunities for understanding microscopic conduction mechanisms in π-conjugated molecules.