Unveiling the topology of partially disordered micro-crystalline nitro-perylenediimide with X-aggregate stacking: an integrated approach.

Profound knowledge of the molecular structure and supramolecular organization of organic molecules is essential to understand their structure-property relationships. Herein we demonstrate the packing arrangement of partially disordered nitro-perylenediimide (NO-PDI), revealing that the perylenediimide units exhibit an X-shaped packing pattern. The packing of NO-PDI is derived using a complementary approach that utilises solid-state NMR (ssNMR) and 3D electron diffraction (3D ED) techniques. Perylenediimide (PDI) molecules are captivating due to their high luminescence efficiency and optoelectronic properties, which are related to supramolecular self-assembly. Increasing the alkyl chain length on the imide substituent poses a more significant challenge in crystallizing the resulting molecule. In addition to the alkyl tails, other functional groups, like the nitro group attached as a bay substituent, can also cause disorder. Such heterogeneity could lead to diffuse scattering, which then complicates the interpretation of diffraction experiment data, where perfect periodicity is expected. As a result, there is an unmet need to develop a methodology for solving the structures of difficult-to-crystallize materials. A synergistic approach is utilised in this manuscript to understand the packing arrangement of the disordered material NO-PDI by making use of 3D ED, ssNMR and density functional theory calculations (DFT). The combination of these experimental and theoretical approaches provides great promise in enabling the structural investigation of novel materials with customized properties across various applications, which are, due to the internal disorder, very difficult to study by diffraction techniques. By effectively addressing these challenges, our methodology opens up new avenues for material characterization, thereby driving exciting advancements in the field.