Liquid-Solid interfaces

The formation of self-assembled monolayers at the solid−liquid interface occurs in conditions that are typically close to thermodynamic equilibrium. Moreover, the development of 2D surface-confined networks is largely governed by the same interactions and the same principles of supramolecular chemistry that operate, for example, in medicinal chemistry or 3D solid-state materials.

Thus, investigating the arrangement of molecular building blocks within the resultant 2D networks gives insight into the structural role and the competition and/or cooperation of the intermolecular interactions at play. Furthermore, the possibility offered by STM of doing so on individual molecules, offers a unique opportunity of studying these fundamental interactions (governing also more general 3D supramolecular chemistry) at a level that is not accessible by other analytical techniques.

In particular, we systematically analyse the interplay between coexisting prototypical non-covalent interactions (such as, for example, hydrogen and halogen bonding) in order to determine their structural relevance in the formation of 2D supramolecular structures. In this endeavour, we often collaborate with computational colleagues, since our precise determination of the self-assembled supramolecular nanostructures represents an ideal experimental benchmark for their computational tools.

STM images showing the coassembly of 4MeTFBA and 4TPTZ at the 1-phenyloctane/HOPG interface (a) without coronene inclusion and (c) with coronene inclusion. The proposed models for the assembly are shown in (b) and (d), respectively [1.]

Key publications:

  1. Determining the relative structural relevance of halogen and hydrogen bonds in self-assembled monolayers
    H. Pinfold, M. Sacchi, G. Pattison and G. Costantini
    J. Phys. Chem C. 125, 27784 (2021).
  2. Fluorinated Carboxylic Acids as Powerful Building Blocks for the Formation of Bimolecular Monolayers
    H. Pinfold, C. Greenland, G. Pattison, and G. Costantini
    Chem. Commun. 56, 125 (2019).
  3. High Quality Dispersions of Hexabenzocoronene in Organic Solvents
    J.M. Hughes, Y. Hernandez, D. Aherne, L. Doessel, K. Müllen, B. Moreton, T.W. White, C. Partridge, G. Costantini, A. Shmeliov, M. Shannon, V. Nicolosi, and J.N. Coleman
    J. Am. Chem. Soc. 134, 12168 (2012).
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