Solvatomorphism of a 2,6-pyridyldicarboxamide-based foldamer

A detailed solvatomorphism study conducted on a diamine-terminated 2,6-pyridyldicarboxamide-based foldamer 1 is reported. This investigation establishes the influence of a diverse range of polar and non-polar solvents including chloroform (1A), a trifluorotoluene/dichloromethane mixture (1A), dimethylformamide/diethyl ether (1B), tetrahydrofuran (1·THF), butanone (1·butanone), dichloromethane (1·DCM), a methanol/dichloromethane mixture (1·MeOH) and dimethylsulfoxide (1·DMSO) on the solid-state conformation and crystal packing behaviour of this supramolecular scaffold. Single-crystal X-ray diffraction analysis of the seven solvatomorphs of the studied foldamer (1A, 1B, 1·DCM, 1·THF, 1·butanone, 1·MeOH and 1·DMSO) identified that 1·DCM, 1·THF, 1·butanone, 1·MeOH and 1·DMSO form supramolecular aggregates (<i>e.g.</i>, channels/cavities) which incorporate solvent molecules within the voids of the system, leading them to adopt channels of differing dimensions between 3.5 and 9.0 Å. Solid-state analysis identified that a diverse array of intermolecular non-covalent interactions form between the foldamer and the solvent molecule, including N-H⋯O, N-H⋯Cl, O-H⋯O, N-H⋯Cl and C-H⋯O hydrogen-bonding interactions, stabilising the formation of these solvent-mediated channel aggregates within the different solvatomorphs of the studied foldamer. We envisage that these solvatomorphism studies will facilitate the future design of foldamers, particularly given the emerging solid-state applications of foldamers which could hold relevance in the field of crystal engineering or for the uptake of small molecules for long-term use in energy storage and materials chemistry.