Two-dimensional crystal engineering using halogen and hydrogen bonds: towards structural landscapes

Two-dimensional (2D) crystallization on solid surfaces is governed by a subtle balance of supramolecular and interfacial interactions. However, these subtle interactions often make the prediction of supramolecular structure from the molecular structure impossible. As a consequence, surface-based 2D crystallization has often been studied on a case-by-case basis, which hinders the identification of structure-determining relationships between different self-assembling systems. Here we begin the discussion on such structure-determining relationships by comparing the 2D crystallization of two identical building blocks based on a 1,3,5-tris(pyridine-4-ylethynyl)benzene unit at the solution-solid interface. The concepts of supramolecular synthons and structural landscapes are introduced in the context of 2D crystallization on surfaces to identify common structural elements. The systems are characterized using scanning tunneling microscopy (STM). This strategy involves carrying out minor structural modifications on the parent compound to access supramolecular patterns that are otherwise not obtained. We demonstrate that this chemical perturbation strategy translates equally well for 2D co-crystallization experiments with halogen bond donors yielding porous bi-component networks. The holistic approach described here represents a stepping stone towards gaining predictive power over the 2D crystallization of molecules on solid surfaces.