Self‐Assembling Behaviour of Perylene, Perylene Diimide, and Thionated Perylene Diimide Deciphered through Non‐Covalent Interactions

The π-conjugated supramolecular polymers (SMP) have gained vast popularity in materials chemistry and biomedicine due to their spectacular self-assembling behaviour. A detailed account of the electronic structure and bonding through quantum theory of atoms-in-molecules, non-covalent interactions, and energy decomposition analysis (EDA) in the oligomers of perylene, perylene diimide (PDI), and thionated-PDI (t-PDI) is presented. The oligomers of all three molecules show a slip angle of θ≈62° thus forming H-aggregates. The stacking pattern in perylene oligomers prefers a slip-stacked brick-layer order, while the bulkier PDI and t-PDI prefer a parallel step-wise pattern in their oligomers. Successive addition of monomers leads to a consequent rise in the association energy, although to a much greater extent in PDI and t-PDI than in perylene. While the major contribution to this association energy comes from the dispersion interactions in all three systems, the steric interactions in t-PDI quench the cooperativity in its SMP formation. A detailed analysis of the non-covalent interactions reveals the presence of π-π, π-hole⋅⋅⋅O=C, and π-hole⋅⋅⋅S=C electrostatic interactions playing a crucial role in the self-assembly process, which can be further implemented on developing force field-based methods for understanding the self-assembling mechanism in higher degree of oligomers.