Hydrogen bond‐Driven Self–Assembly between Amidinium Cations and Carboxylate Anions: A Combined Molecular Dynamics, NMR Spectroscopy, and Single Crystal X‐ray Diffraction Study

A combination of molecular dynamics (MD), NMR spectroscopy, and single crystal X-ray diffraction (SCXRD) techniques was used to probe the self–assembly of para- and meta-bis(amidinium) compounds with para-, meta-, and ortho-dicarboxylates. Good concordance was observed between the MD and experimental results. In DMSO solution, the systems form several rapidly exchanging assemblies, in part because a range of hydrogen bonding interactions is possible between the amidinium and carboxylate moieties. Upon crystallization, the majority of the systems form 1D supramolecular polymers, which are held together by short N−H⋅⋅⋅O hydrogen bonds.