0000000000242584
AUTHOR
Christopher M. Hauke
On-surface covalent linking of organic building blocks on a bulk insulator.
On-surface synthesis in ultrahigh vacuum provides a promising strategy for creating thermally and chemically stable molecular structures at surfaces. The two-dimensional confinement of the educts, the possibility of working at higher (or lower) temperatures in the absence of solvent, and the templating effect of the surface bear the potential of preparing compounds that cannot be obtained in solution. Moreover, covalently linked conjugated molecules allow for efficient electron transport and are, thus, particularly interesting for future molecular electronics applications. When having these applications in mind, electrically insulating substrates are mandatory to provide sufficient decoupli…
Molecular Self-Assembly of Enantiopure Heptahelicene-2-Carboxylic Acid on Calcite (1014)
Chirality can have a decisive influence on the molecular structure formation upon self-assembly on surfaces. In this paper, we study the structures formed by enantiopure (M)-heptahelicene-2-carboxylic acid ((M)-[7]HCA) on the calcite (10 (1) over bar4) cleavage plane under ultrahigh vacuum conditions. Previous noncontact atomic force microscopy studies have revealed that the racemic mixture of (M)-[7]HCA and (P)-[7]FICA (1:1) self-assembles into well-defined molecular double rows that are oriented along the calcite [01 (1) over bar0] direction. Here, we investigate the enantiopure (M)[7]HCA compound, resulting in distinctly different molecular structures upon deposition onto calcite (10 (1)…
One-Pot Synthesis and AFM Imaging of a Triangular Aramide Macrocycle
Macrocyclizations in exceptionally good yields were observed during the self-condensation of N-benzylated phenyl p-aminobenzoates in the presence of LiHMDS to yield three-membered cyclic aramides that adopt a triangular shape. An ortho-alkyloxy side chain on the N-benzyl protecting group is necessary for the macrocyclization to occur. Linear polymers are formed exclusively in the absence of this Li-chelating group. A model that explains the lack of formation of other cyclic congeners and the demand for an N-(o-alkoxybenzyl) protecting group is providedon the basis of DFT calculations.High-resolution AFM imaging of the prepared molecular triangles on a calcite(10.4) surface shows individual …
Controlling Molecular Self-Assembly on an Insulating Surface by Rationally Designing an Efficient Anchor Functionality That Maintains Structural Flexibility
Molecular self-assembly on surfaces is dictated by the delicate balance between intermolecular and molecule-surface interactions. For many insulating surfaces, however, the molecule-surface interactions are weak and rather unspecific. Enhancing these interactions, on the other hand, often puts a severe limit on the achievable structural variety. To grasp the full potential of molecular self-assembly on these application-relevant substrates, therefore, requires strategies for anchoring the molecular building blocks toward the surface in a way that maintains flexibility in terms of intermolecular interaction and relative molecule orientation. Here, we report the design of a site-specific anch…