Sequential nested assembly at the liquid/solid interface

Abstract

Studying the stepwise assembly of a four component hybrid structure on Au(111)/mica, the pores of a hydrogen bonded bimolecular network of 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) and 1,3,5-triazine-2,4,6-triamine (melamine) were partitioned by three and four-armed molecules based on oligo([biphenyl]-4-ylethynyl)benzene, followed by the templated adsorption of either C60 fullerene or adamantane thiol molecules. The characterisation by ambient scanning tunneling microscopy (STM) reveals that the pore modifiers exhibit dynamics which pronouncedly depend on the molecular structure. The three-armed molecule 1,3,5-tris([1,1′-biphenyl]-4-ylethynyl)benzene (3BPEB) switches between two symmetry equivalent configurations on a time scale fast compared to the temporal resolution of the STM. Derivatisation of 3BPEB by hydroxyl groups substantially reduces the switching rate. For the four-armed molecule configurational changes are observed only occasionally. The observation of isolated fullerenes and small clusters of adamantane thiol molecules, which are arranged in a characteristic fashion, reveals the templating effect of the trimolecular supramolecular network. However, the fraction of compartments filled by guest molecules is significantly below one for both the thermodynamically controlled adsorption of C60 and the kinetically controlled adsorption of the thiol with the latter causing partial removal of the pore modifier. The experiments, on the one hand, demonstrate the feasibility of templating by nested assembly but, on the other hand, also pinpoint the requirement for the energy landscape to be tolerant to variations in the assembly process.

Self-Accommodating Honeycomb Networks from Supramolecular Self-Assembly of s-Indacene-tetrone on Silver Surfaces

“…On the basis of these observations, and by analogy with the HC1 network on Ag(100) described above, we can postulate that type A corresponds to single molecules that are trapped within the honeycomb framework cavities and that can freely rotate between two metastable positions that are 90° rotated with respect to each other. As a result, the apparent square-shaped STM contrast corresponds to the average occupation position, similar to other studies displaying dynamic systems. ,, …”

“…As a result, the apparent square-shaped STM contrast corresponds to the average occupation position, similar to other studies displaying dynamical systems. 13,26,27 Careful inspection of the vacancy defects within this structure allowed confirming the presence of only one molecule per cavity. As highlighted by the colored circles in Fig.…”

“…As a result, the apparent square-shaped STM contrast corresponds to the average occupation position, similar to other studies displaying dynamic systems. 13,26,27 Careful inspection of the vacancy defects within this structure allowed confirmation of the presence of only one molecule per cavity. As highlighted by the colored circles in Figure 2b, defects are preferentially found inside the cavities and appear as empty (green) or fuzzy pores (yellow), as well as a single elongated bright STM feature of the same shape and dimension as type B ones, but with a different molecular contrast (blue circles).…”

Stepwise Adsorption of Alkoxy‐Pyrene Derivatives onto a Lamellar, Non‐Porous Naphthalenediimide‐Template on HOPG

“…Although the necessity to induce surface adhesion through chemical design may limit the options to explore, surface‐supported multicomponent supramolecular systems were realized resorting to a limited number of strategies. In particular, porous self‐assembled monolayers have received attention because of their preorganization [26–39] . One of the most attractive features of this approach is its modularity, which allows control over pore size and, hence, molecular dimensions of the trapped guests [39–45] .…”

“…In particular, porouss elf-assembled monolayers have received attention because of their preorganization. [26][27][28][29][30][31][32][33][34][35][36][37][38][39] One of the mosta ttractive features of this approachi si ts modularity,w hich allows control over pore size and, hence,m olecular dimensions of the trapped guests. [39][40][41][42][43][44][45] Other reports have provided alternative strategies based on host-guesti nteractions with metal complexes.…”