Leveraging the relative strengths of hydrogen and halogen bonds to control nanostructures

Halogen bonds (XBs) and hydrogen bonds (HBs) present a straightforward yet effective strategy for controlling nanostructure morphology. The self-assembled nanopattern, modulated by the relative strengths of XBs and HBs, has rarely been studied using analogous molecules. This research systematically evaluates the relationship between the strengths of Br···O hetero-XBs and N···H HBs in directing the formation of 2D supramolecular co-assembled structures. In this work, tetracarboxylic acid (PEDA), featuring four carboxyl substitutions, forms a stable hydrogen-bonded Rosette network that can function as a template for trapping guest molecules of complementary shape and size. The star-shaped bromine-substituted 1,3,5-tris(3,5-dibromophenyl)benzene (TDB) and 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT) serve as XB donor and HB acceptor respectively, thus capable of acting as guest molecules co-assembly with the PEDA at the heptanoic acid/HOPG interface. Bimolecular co-assembly patterns resulting from these combinations were investigated using scanning tunneling microscopy (STM) and supported by density functional theory (DFT) calculations. The findings indicate that TDB molecules can be accommodated within the triangular cavities of the Rosette network due to the weaker Br···O hetero-XB. Concurrently, the similar star-shaped TPT can co-assemble with PEDA to form an acid–pyridine–acid Ladder-like network based on stronger N···H HBs. Therefore, Br···O hetero-XBs seemingly play no decisive role in the coassembly process of PEDA and TDB. Conversely, N···H HBs hold evident significance in the coassembly of PEDA and TPT. This work potentially holds substantial value for the future design and customization of devices employing the interplay of XBs and HBs.