Abstract
Noncovalent interactions form the basis of matter and life yet are difficult to characterize. Here we devised a platform strategy to systematically build noncovalent interactions with selective chemical groups into precisely designed configurations by using metal-organic frameworks (MOF) as the molecular scaffold. Using the vibrational Stark effect benchmarked against computer models, we found the electric field provides a unifying metric for quantifying diverse noncovalent interactions in MOFs and solutions. By synthetically making and spectroscopically testing a collection of noncovalent interactions using a nitrile probe, we identified stabilizing fields as strong as -123 MV/cm produced additively by multiple hydrogen bonds, an unusual destabilizing field of +6 MV/cm between antiparallel dipoles , anomalous hydrogen-bond blueshifts as large as 34 cm-1, and unique solvation under nanoconfinement. This method for making and testing noncovalent interactions opens new avenues for exploring the universe of noncovalent interactions.
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