Computational Study of the Molecular Structure and Hydrogen Bonding in the Hamilton Wedge/Cyanuric Acid Binding Motif

Intermolecular binding between a Hamilton wedge and cyanuric acid, a frequently employed binding motif to achieve self-assembly of single-chain polymer nanoparticles, is studied by means of ab initio quantum-chemical and DFT calculations. A conformational analysis of the isolated compounds and the hydrogen-bonded complex reveals several low-energy structures, which are characterized based on their nonplanarity and binding energy. New hypothetical binding motifs are proposed and proven to possess a superior binding energy, upon becoming planar. Comparison to experimentally measured NMR spectroscopy data is made and cases of disagreement are traced back to solvent effects for isolated substituents or to thermally stretched intermolecular bonds for hydrogen-bonded species. Strong linear correlations between NMR chemical shifts and hydrogen-bond lengths are established for all compounds investigated.