Self-Assembly of Discrete Oligomers of Naphthalenediimides in Bulk and on Surfaces

Here, we report on the synthesis of discrete oligomers of alkyl-bridged naphthalenediimides (NDIs) and study their molecular nanostructures both in bulk, in solution, and at the liquid-solid interface. Via an iterative synthesis method, multiple NDI cores were bridged with short and saturated alkyl-diamines (C3 and C12) or long and unsaturated alkyl-diamines (u2C33 to u8C100) at their imide termini. The strong intermolecular interaction between the NDI cores was observed by probing their photophysical properties in solution. In bulk, the discrete NDI oligomers preferentially ordered in lamellar morphologies, irrespective of whether a saturated or unsaturated spacer was employed. Moreover, both the molecular architecture as well as the crystallization conditions play a significant role in the nanoscale ordering. The long unsaturated alkyl chains lead preferably to folded-chain conformations while their saturated analogues form stretched arrangements. At the solution-solid interface, well-defined lamellar regions were observed. These results show that precision in chemical structure alone is not sufficient to reach well-defined structures of discrete oligomers, but that it must be combined with precision in processing conditions. Discrete oligomers of alkyl-bridged naphthalenediimides were synthesized and found to assemble into lamellar morphologies in bulk and at the liquid-solid interface. The results show that both the molecular architecture as well as the crystallization condition play a significant role in the nanoscale ordering and raise the question of the trade-off between synthetic efforts and novel properties of molecularly perfect materials.image