How to achieve self-assembly in polar solvents based on specific interactions? Some general guidelines

Abstract

In general, self-assembly in polar solutions requires a combination of several non-covalent interactions within one binding motif. Besides the combination of H-bonds and hydrophobic or aromatic stacking interactions, in the last few years H-bonded ion pairs have been proven useful in this context. Also the molecular rigidity and the extent of intra- versus intermolecular interactions within the monomer play an important role in determining the self-assembling properties of a given monomer. We present some general guidelines and illustrative examples of various approaches that have been pursued in the literature before finally concentrating on a case study from our own work, the dimerization of a guanidiniocarbonyl pyrrole carboxylate zwitterion. This zwitterion forms stable dimers with K > 10⁹ M⁻¹ in DMSO and >10² M⁻¹ even in water and can not only be used to study the importance of various non-covalent interactions for self-assembly in polar solvents but also to construct large nanostructures.