Resonant Electron Tunneling Induces Isomerization of π‐Expanded Oligothiophene Macrocycles in a 2D Crystal

Abstract Macrocyclic oligothiophenes and their π‐expanded derivatives constitute versatile building blocks for the design of (supra)molecularly engineered active interfaces, owing to their structural, chemical, and optoelectronic properties. Here, it is demonstrated how resonant tunneling effect induces single molecular isomerization in a 2D crystal, self‐assembled at solid–liquid interfaces under ambient conditions. Monolayers of a series of four π‐expanded oligothiophene macrocycles are investigated by means of scanning tunneling microscopy and scanning tunneling spectroscopy (STS) at the interface between their octanoic acid solutions and the basal plane of highly oriented pyrolytic graphite. Current–voltage characteristics confirm the donor‐type character of the macrocycles, with the highest occupied molecular orbital and the lowest unoccupied molecular orbital (LUMO) positions consistent with time‐dependent density functional theory calculations. Cyclic STS measurements show the redox isomerization from Z,Z‐8T6A to its isomer E,E‐8T6A occurring in the 2D crystal, due to the formation of a negatively charged species when the tunneling current is in resonance with the LUMO of the macrocycle.