Effect of aromatic substituents on the H-bonded assembly of diketopyrrolopyrroles at solid-liquid interfaces

Hydrogen-bonded (H-bonded) self-assembly is a suitable approach for tailoring the solid-state packing and properties of organic semiconductors. Here we studied the H-bonded self-assembly of an important class of organic semiconductors, diketopyrrolopyrrole (DPP) derivatives, diselenophenylDPP (DSeDPP), dithiazolylDPP (DTzDPP), and dithienothiophenylDPP (DTTDPP), at solid-liquid interfaces using scanning tunneling microscopy (STM) and density functional theory (DFT). At the 1-octanoic acid/highly ordered pyrolytic graphite (HOPG) interface, DSeDPP and DTzDPP either co-assemble with the solvent via H-bonding between lactam and carboxyl groups or form homoassemblies through H-bonding between the lactam groups. However, DTTDPP forms two different homoassemblies involving H-bonding between lactam groups or weak H-bonding between the lactam group and the heteroaromatic ring. Enthalpic factors for the formation of homoassemblies and co-assemblies are investigated by evaluating the inter- and intramolecular interactions in the self-assembled lattices using DFT. A homoassembly with a twisted geometry of molecules with intermolecular pi-interactions is only observed for DSeDPP. The absence of homoassembly with the twisted geometry of DTzDPP is attributed to the higher strain energy required to acquire out-of-plane twists in this molecule. Our study shows the profound effects aromatic substituents can impart in the supramolecular assembly of DPP molecules, which influences film morphology and hence its properties (e.g. charge transport). Planar and twisted self-assemblies of diketopyrrolopyrrole molecules are determined by aromatic substitutions as revealed by STM at solid-liquid interfaces.