Electrostatic atlas of non-covalent interactions built into metal–organic frameworks

Non-covalent interactions are central to the organization of matter and molecular recognition processes, yet they are difficult to characterize. Here we devise a platform strategy to systematically build non-covalent interactions with selective chemical groups into precisely designed configurations by using metal-organic frameworks (MOFs) as the molecular scaffold. Using the vibrational Stark effect benchmarked against computer models, we find the electric field provides a unifying metric for quantifying diverse non-covalent interactions in MOFs and solvation environments. We synthesize and analyse spectroscopically a collection of non-covalent interactions using a nitrile probe within the MOF structure, and identify stabilizing fields as strong as -123 MV cm-1 produced additively by multiple hydrogen bonds, an unusual destabilizing field of +6 MV cm-1 between antiparallel dipoles, anomalous hydrogen-bond blueshifts as large as 34 cm-1 and unique solvation under nanoconfinement. This method for making and testing non-covalent interactions opens new avenues for exploring non-covalent interactions.