We measured photoinduced charge separation in isolated individual C60-tethered 2,5-dithienylpyrrole triad (C60 triad) molecules with submolecular resolution using a custom-built laser-assisted scanning tunneling microscope. Laser illumination was introduced evanescently into the tunneling junction through total internal reflection, and the changes in tunneling current and electronic spectra caused by photoexcitation were measured and spatially resolved. Photoinduced charge separation was not detected for all C60 triad molecules, indicating that the conformations of the molecules may affect the excitation probability, lifetime, and/or charge distribution. A photoinduced signal was not observed for dodecanethiol molecules in the surrounding matrix or for control molecules without C60 moieties, as neither absorbs incident photons at this energy. This spectroscopic imaging technique has the potential to elucidate detailed photoinduced carrier dynamics, which are inaccessible via ensemble-scale (i.e., averaging) measurements, which can be used to direct the rational design and optimization of molecular p-n junctions and assemblies for energy harvesting.

Understanding electron transfer at the molecular level is critical to the rational design and performance improvement of organic optoelectronics and photovoltaics. The behavior of photoactive molecules depends critically on their local environment and defects present in the surface. Here, we use a custom-built, laser-assisted scanning tunneling microscope to probe the photocurrent of isolated anthracene derivates on Au {111}. The photocurrent originates from charge-transfer transitions of anthracene into an excited state when illuminated by an evanescent field. The influence of the image potential states on terraces and at defects in the gold surface on photo-induced charge transfer will be discussed.

When alkanethiolate self-assembled monolayers on Au{111} are exchanged with alkaneselenols from solution, replacement of thiolates by selenols is rapid and complete, and is well described by perimeter-dependent island growth kinetics. The monolayer structures change as selenolate coverage increases, from being epitaxial and consistent with the initial thiolate structure to being characteristic of selenolate monolayer structures. At room temperature and at positive sample bias in scanning tunneling microscopy, the selenolate-gold attachment is labile, and molecules exchange positions with neighboring thiolates. The scanning tunneling microscope probe can be used to induce these place-exchange reactions.

When alkanethiolate self-assembled monolayers on Au{111} are exchanged with alkaneselenols from solution, replacement of thiolates by selenols is rapid and complete, and is well described by perimeter-dependent island growth kinetics. The monolayer structures change as selenolate coverage increases, from being epitaxial and consistent with the initial thiolate structure to being characteristic of selenolate monolayer structures. At room temperature and at positive sample bias in scanning tunneling microscopy, the selenolate-gold attachment is labile, and molecules exchange positions with neighboring thiolates. The scanning tunneling microscope probe can be used to induce these place-exchange reactions.

Dihydroazulenes are photochromic molecules that reversibly switch between two distinct geometric and conductivity states. Molecular design, surface attachment, and precise control over the assembly of such molecular machines are critical in order to understand molecular function and motion at the nanoscale. Here, we use surface-enhanced Raman spectroscopy on special atomically flat, plasmonically enhanced substrates to measure the photoreaction kinetics of isolated dihydroazulene-functionalized molecules assembled on Au{111}, which undergo a ring-opening reaction upon illumination with UV light and switch back to the initial isomer via thermal relaxation. Photokinetic analyses reveal the high efficiency of the dihydroazulene photoreaction on solid substrates compared to other photoswitches. An order of magnitude decrease in the photoreaction cross section of surface-bound dihydroazulenes was observed when compared with the cross sections of these molecules in solution.

Self-assembled monolayers are a unique class of nanostructured materials, with properties determined by their molecular lattice structures, as well as the interfaces with their substrates and environments. As with other nanostructured materials, defects and dimensionality play important roles in the physical, chemical, and biological properties of the monolayers. In this review, we discuss monolayer structures ranging from surfaces (two-dimensional) down to single molecules (zero-dimensional), with a focus on applications of each type of structure, and on techniques that enable characterization of monolayer physical properties down to the single-molecule scale.

We identify and control the photoreaction paths of self-assembled monolayers (SAMs) of thiolate-linked anthracene phenylethynyl molecules on Au substrate surfaces, and study the effects of nanoscale morphology of substrates on regioselective photoreactions. Two types of morphologies, atomically flat and curved, are produced on Au surfaces by controlling substrate structure and metal deposition. We employ surface-enhanced Raman spectroscopy (SERS), combined with Raman mode analyses using density functional theory, to identify the different photoreaction paths and to track the photoreaction kinetics and efficiencies of molecules in monolayers. The SAMs on curved surfaces exhibit dramatically lower regioselective photoreaction kinetics and efficiencies than those on atomically flat surfaces. This result is attributed to the increased intermolecular distances and variable orientations on the curved surfaces. Better understanding of the morphological effects of substrates will enable control of nanoparticle functionalization in ligand exchange in targeted delivery of therapeutics and theranostics and in catalysis.