Highly nonlinear transport across single-molecule junctions via destructive quantum interference

To rival the performance of modern integrated circuits, single-molecule devices must be designed to exhibit extremely nonlinear current-voltage (I-V) characteristics^1-4. A common approach is to design molecular backbones where destructive quantum interference (QI) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) produces a nonlinear energy-dependent tunnelling probability near the electrode Fermi energy (E_F)^5-8. However, tuning such systems is not straightforward, as aligning the frontier orbitals to E_F is hard to control⁹. Here, we instead create a molecular system where constructive QI between the HOMO and LUMO is suppressed and destructive QI between the HOMO and strongly coupled occupied orbitals of opposite phase is enhanced. We use a series of fluorene oligomers containing a central benzothiadiazole¹⁰ unit to demonstrate that this strategy can be used to create highly nonlinear single-molecule circuits. Notably, we are able to reproducibly modulate the conductance of a 6-nm molecule by a factor of more than 10⁴.