The interlayer interactions of two-dimensional covalent organic frameworks (2D COFs) are important for their formation but are ultimately poorly understood. An advanced understanding will help inform better control of the growth process and fabricate materials with higher crystallinity. Adapting the monomer design criteria, we have synthesized hexagonal imine-linked macrocycles that self-assemble into nanotubes and act as soluble structural analogs of 2D COFs. By introducing chirality via pendant side chains, we study the thermodynamics of macrocycle aggregation by variable temperature circular dichroism and UV-vis spectroscopy. We show that that electron-donating substituents in the macrocycle backbone lead to enhanced stacking enthalpies, offering experimental support for previously reported calculations. The study of macrocycle self-assembly sheds insight into some of the fundamental stacking interactions of the extended 2D COF layers and will be used to inform future monomer design.

Self-assembly of imine-linked macrocycles related to 2D covalent organic frameworks

256th National Meeting (2018)

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