Halogen Bonded Assemblies of Arylene-imides and -diimides: Insight from Electronic, Structural and Computational studies

Halogen bonding interactions in electron deficient π-scaffolds has largely been underexplored. Herein, we have studied the halogen bonding properties of arylene-imide/-diimide-based electron deficient scaffolds. We probed the influence of: scaffold size, e.g. from small phthalimide (PTMI), moderately-sized pyromelliticdiimide (PMDI) or naphthalenediimides (NDIs) to large perylenediimide (PDI); axial-group modifications; varied number of halogens, etc. on the halogen bonding and its self-assembly in a set of nine molecules. The structural modification leads to tunable optical as well as redox property. Gratifyingly, we realized single crystals of all the nine systems, which revealed Br∙∙∙O, Br∙∙∙Br or Br∙∙∙π halogen bonding interactions, with few systems capable of forming all the three-types. These interactions lead to halogen bonded rings (up to 12-membered), which propagate to form stacked 1D-, 2D- or corrugated sheets. We also identified few outliers, e.g. molecule which prefer C-H∙∙∙O hydrogen bonding over halogen bonding; or a non-centrosymmetric organization over the centrosymmetric ones. Computational studies based on Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) analysis provided
further insight into the halogen bonding interactions. This study can lead to a predictive design tool-box to further explore related systems on surfaces reinforced by these weak directional forces.