Hierarchical formation of helical supramolecular polymers via stacking of hydrogen-bonded pairs in water

Abstract

Bifunctional ureido- s -triazines provided with penta(ethylene oxide) side chains are able to self assemble in water, leading to helical columns via cooperative stacking of the hydrogen-bonded pairs (DADA array). Monofunctional ureido- s -triazines do not form such helical architectures. The presence of a linker, covalently connecting the two ureido- s -triazine units, is essential as it generates a high local concentration of aromatic units, favorable for stacking interactions. This hydrophobic stacking of the aromatic units occurs at concentrations as low as 5⋅10 −6 M and can be visualized by using fluorescence spectroscopy. The stacking generates a hydrophobic microenvironment that allows intermolecular hydrogen bonding to occur at higher concentrations because the hydrogen bonds are shielded from competitive hydrogen bonding with water. This hierarchical process results in the formation of a helical self-assembled polymer in water at concentrations above 10 −4 M. Chiral side chains attached to the ureido- s -triazine units bias the helicity of these columns as concluded from CD spectroscopy and “Sergeants and Soldiers” experiments.