Utilizing “latent” carbon: Repositioning hydrogen‐bonded synthons and assemblies via halogen bonding to π‐systems

Abstract

Molecules bearing carboxylic acid, amide, and hydroxyl groups are ubiquitous in crystal engineering, where robust hydrogen‐bonded synthons centred on these functionalities enable reliable crystal structure design. We now show that halogen bonding to the carbon π‐system of such molecules, traditionally ignored in crystal engineering, permits the recognition and directional assembly of the resulting hydrogen‐bonded structural subunits, leaving the archetypal hydrogen‐bonded ring, ladder, and chain homosynthons intact, but repositioned in space. When applied to heteromolecular synthons, this enables rearranging more complex hydrogen‐bonded motifs and the evolution of binary cocrystals into ternary ones through “latent” carbon‐based recognition sites, demonstrating a rational approach to build higher‐order solid‐state supramolecular assemblies.