As chemistry converges on a complete understanding of the nature of the covalent bond, it has become clear that turning attention towards the nature of non-covalent interactions is vital for developing, controlling, and understanding complex chemical systems. Intermolecular interactions involving halogen atoms—"halogen-bonding” (XB) interactions—are prolific in contemporary literature regarding self-organization and nanotechnology development. XB interactions between two halogens (X…X) have even greater potential here, as the relative weakness of their interaction allows for fine-tuning of molecularly assembled structures. The work presented here probes the nature of X…X bonds in self-assembled monolayers, combining experimental data from surface imaging with insight gained from X…X bonding model simulations in silico. Experiments with scanning tunneling microscopy (STM) allows for the direct assessment of monolayer morphology and X…X bond lengths as a function of parameters such as temperature, halogen identity, surface identity, etc. Hexahalotriphenylenes are used as the model analytes for STM imaging. The in silico experiments accommodate a wider scope of haloarenyl substrates to study X…X bonding, using non-periodic and periodic density functional theory (DFT) calculations performed with Gaussian 16 andVienna Ab Initio Simulation Packages (VASP) respectively. VASP calculations allow for the exploration of the impact of substrate adsorption on surfaces common in self-assembly literature, like highly ordered pyrolytic graphite, gold(111), and silver(110).

In silico and tunneling microscopy investigations of surface impact on halogen…halogen intermolecular forces

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