Isomerization reactions on single adsorbed molecules

Molecular switches occur throughout nature. In one prominent example, light induces the isomerization of retinal from the compact 11-cis form to the elongated all-trans form, a conversion that triggers the transformation of light into a neural impulse in the eye. Applying these natural principles to synthetic systems offers a promising way to construct smaller and faster nanoelectronic devices. In such systems, electronic switches are essential components for storage and logical operations. The development of molecular switches on the single-molecule level would represent a major step toward incorporating molecules as building units into nanoelectronic circuits. Molecular switches must be both reversible and bistable. To meet these requirements, a molecule must have at least two different thermally stable forms and a way to repeatedly interconvert between those forms based on changes in light, heat, pressure, magnetic or electric fields, pH, mechanical forces, or electric currents. The conversion should be connected to a measurable change in electronic, optical, magnetic, or mechanical properties. Because isomers can differ significantly in physical and chemical properties, isomerization could serve as a molecular switching mechanism. Integration of molecular switches into larger circuits will probably require arranging them on surfaces, which will require a better understanding of isomerization reactions in these environments. In this Account, we describe our scanning tunneling microscopy studies of the isomerization of individual molecules adsorbed on metal surfaces. Investigating chlorobenzene and azobenzene derivatives on the fcc(111) faces of Ag, Cu, and Au, we explored the influence of substituents and the substrate on the excitation mechanism of the isomerization reaction induced by inelastically tunneling electrons. We achieved an irreversible configurational (cis-trans) isomerization of individual 4-dimethyl-amino-azobenzene-4-sulfonic acid molecules on Au(111), a reversible configurational (cis-trans) isomerization of amino-nitro-azobenzene on Au(111), a constitutional (meta-ortho) isomerization of chloronitrobenzene molecules adsorbed on Cu(111) and Au(111), and a constitutional (meta-para) isomerization of dichlorobenzene molecules adsorbed on Cu(111) and Ag(111). These studies demonstrate that we can induce a variety of isomerization reactions by electron excitation on a metal surface. Our model isomerization studies provide a way to manipulate properties of single molecules, changing both their geometric structure and their physicochemical properties. The control of isomerization of single molecules will advance the development of single-molecule electronics and other nanoscale processes.