Computer Simulations of Surface-Confined Cocrystals Cemented by 3-Fold Halogen Bonds

The halogen bonds (XBs) are attractive, anisotropic noncovalent interactions with great potential in crystal engineering on solid surfaces. Therefore, in this contribution, we used lattice Monte Carlo simulations to investigate the surface-assisted formation of low-dimensional nanoporous networks cemented by directional 3-fold XBs. Specifically, in the adsorbed overlayers comprising mixed rod-like and star-shaped organic molecules, we observed the self-assembly of a series of hierarchically organized two-dimensional (2D) cocrystals with scalable morphological properties, such as chirality, molecular packing, density, and porosity. The structural integrity of the simulated assemblies was confirmed through radial distribution function analysis and 2D Voronoi diagrams. The theoretically predicted supramolecular patterns are aesthetically pleasing and have potential applications in the rational construction of 2D quantum dot arrays and the precise positioning of guest molecules.