nl7b00596_si_001.pdf (2.2 MB)

# Shuttlecock-Shaped Molecular Rectifier: Asymmetric Electron Transport Coupled with Controlled Molecular Motion

journal contribution

posted on 2017-05-25, 00:00 authored by Taekhee Ryu, Yves Lansac, Yun Hee JangA fullerene
derivative with five hydroxyphenyl groups attached
around a pentagon, (4-HOC

_{6}H_{4})_{5}HC_{60}(**1**), has shown an asymmetric current–voltage (*I*–*V*) curve in a conducting atomic force microscopy experiment on gold. Such molecular rectification has been ascribed to the asymmetric distribution of frontier molecular orbitals over its shuttlecock-shaped structure. Our nonequilibrium Green’s function (NEGF) calculations based on density functional theory (DFT) indeed exhibit an asymmetric*I*–*V*curve for**1**standing up between two Au(111) electrodes, but the resulting rectification ratio (RR ∼ 3) is insufficient to explain the wide range of RR observed in experiments performed under a high bias voltage. Therefore, we formulate a hypothesis that high RR (>10) may come from molecular orientation switching induced by a strong electric field applied between two electrodes. Indeed, molecular dynamics simulations of a self-assembled monolayer of**1**on Au(111) show that the orientation of**1**can be switched between standing-*up*and lying-on-the-*side*configurations in a manner to align its molecular dipole moment with the direction of the applied electric field. The DFT–NEGF calculations taking into account such field-induced reorientation between*up*and*side*configurations indeed yield RR of ∼13, which agrees well with the experimental value obtained under a high bias voltage.