The unique electronic properties and functional tunability of polycyclic aromatic hydrocarbons have recently fostered high hopes for their use in flexible, green, portable, and cheap technologies. Most applications require the deposition of thin molecular films onto conductive electrodes. The growth of the first few molecular layers represents a crucial step in the device fabrication since it determines the structure of the molecular film and the energy level alignment of the metal–organic interface. Here, we explore the formation of this interface by analyzing the interplay between reversible molecule–substrate charge transfer, yielding intermolecular repulsion, and van der Waals attractions in driving the molecular assembly. Using a series of ad hoc designed molecules to balance the two effects, we combine scanning tunnelling microscopy with atomistic simulations to study the self-assembly behavior. Our systematic analysis identifies a growth mode characterized by anomalous coarsening that we anticipate to occur in a wide class of metal–organic interfaces and which should thus be considered as integral part of the self-assembly process when depositing a molecule on a conducting surface.
It's a kind of magic: Hydroxy pentaaryl borazine molecules self-assemble into small clusters (see structure) on Cu(111) surfaces, whereas with symmetric hexaaryl borazine molecules large islands are obtained. Simulations indicate that the observed "magic" cluster sizes result from long-range repulsive Coulomb forces arising from the deprotonation of the B-OH groups of the hydroxy pentaaryl borazine.
Organic charge transfer (CT) complexes obtained by combining molecular electron donors and acceptors have attracted much interest due to their potential applications in organic opto-electronic devices. In order to work, these systems must have an electronic matching - the highest occupied molecular orbital (HOMO) of the donor must couple with the lowest unoccupied molecular orbital (LUMO) of the acceptor - and a structural matching, so as to allow direct intermolecular CT. Here it is shown that, when molecules are adsorbed on a metal surface, novel molecular organizations driven by surface-mediated CT can appear that have no counterpart in condensed phase non-covalent assemblies of donor and acceptor molecules. By means of scanning tunneling microscopy and spectroscopy it is demonstrated that the electronic and self-assembly properties of an electron acceptor molecule can change dramatically in the presence of an additional molecular species with marked electron donor character, leading to the formation of unprecedented core-shell assemblies. DFT and classical force-field simulations reveal that this is a consequence of charge transfer from the donor to the acceptor molecules mediated by the metallic substrate.
Two borazine derivatives have been synthesised to investigate their self-assembly behaviour on Au(111) and Cu(111) surfaces by scanning tunnelling microscopy (STM) and theoretical simulations. Both borazines form extended 2D networks upon adsorption on both substrates at room temperature. Whereas the more compact triphenyl borazine 1 arranges into close-packed ordered molecular islands with an extremely low density of defects on both substrates, the tris(phenyl-4-phenylethynyl) derivative 2 assembles into porous molecular networks due to its longer lateral substituents. For both species, the steric hindrance between the phenyl and mesityl substituents results in an effective decoupling of the central borazine core from the surface. For borazine 1, this is enough to weaken the molecule–substrate interaction, so that the assemblies are only driven by attractive van der Waals intermolecular forces. For the longer and more flexible borazine 2, a stronger molecule–substrate interaction becomes possible through its peripheral substituents on the more reactive copper surface.
It's a kind of magic: Hydroxy pentaaryl borazine molecules self‐assemble into small clusters (see structure) on Cu(111) surfaces, whereas with symmetric hexaaryl borazine molecules large islands are obtained. Simulations indicate that the observed “magic” cluster sizes result from long‐range repulsive Coulomb forces arising from the deprotonation of the BOH groups of the hydroxy pentaaryl borazine.
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