We investigate the thermally-induced cyclization of 1,2 - bis(2 - phenylethynyl)benzene on Au(111) using scanning tunneling microscopy and computer simulations. Cyclization of sterically hindered enediynes is known to proceed via two competing mechan
isms in solution: a classic C1 - C6 or a C1 - C5 cyclization pathway. On Au(111) we find that the C1 - C5 cyclization is suppressed and that the C1 - C6 cyclization yields a highly strained bicyclic olefin whose surface chemistry was hitherto unknown. The C1 - C6 product self-assembles into discrete non-covalently bound dimers on the surface. The reaction mechanism and driving forces behind non-covalent association are discussed in light of density functional theory calculations.
Contributing to the need of new graphene nanoribbon (GNR) structures that can be synthesized with atomic precision, we have designed a reactant that renders chiral (3,1) - GNRs after a multi-step reaction including Ullmann coupling and cyclodehydroge
nation. The nanoribbon synthesis has been successfully proved on different coinage metals, and the formation process, together with the fingerprints associated to each reaction step, has been studied combining scanning tunnelling microscopy, core-level spectroscopy and density functional calculations. In addition to the GNR chiral edge structure, the substantial GNR lengths achieved and the low processing temperature required to complete the reaction grant this reactant extremely interesting properties for potential applications.
A hallmark of quantum control is the ability to manipulate quantum emission at the nanoscale. Through scanning tunneling microscopy induced luminescence (STML) we are able to generate plasmonic light originating from inelastic tunneling processes tha
t occur in a few-nanometer thick molecular film of C$_{60}$ deposited on Ag(111). Single photon emission, not of excitonic origin, occurs with a 1/$e$ lifetime of a tenth of a nanosecond or less, as shown through Hanbury Brown and Twiss photon intensity interferometry. We have performed tight-binding calculations of the electronic structure for the combined Ag-C$_{60}$-tip system and obtained good agreement with experiment. The tunneling happens through electric field induced split-off states below the C$_{60}$ LUMO band, which leads to a Coulomb blockade effect and single photon emission. The use of split-off states is shown to be a general technique that has special relevance for narrowband materials with a large bandgap.
