Pushing the boundaries: The path of mechanosynthesis toward the assembly of supramolecular organic frameworks

Supramolecular organic frameworks (SOFs), synthetic frameworks assembled via non-covalent interactions, are being extensively studied for their applications as porous functional solids endowed with flexibility, reversibility and tunability of stimuli-responsive properties. This review explores the use of mechanosynthesis as a versatile strategy for their rational design and green synthesis, while expanding their structural and functional diversity. After an overview of the path followed by supramolecular mechanochemistry from the assembly of cocrystals to the complexation of host-guest systems in the solid state, we have detailed the mechanosynthesis of hydrogen-bonded organic frameworks (HOFs) and the less-explored halogen-bonded organic frameworks (XOFs), highlighting the advantages of solid-state methods in promoting reactivity, sustainability, and access to otherwise unattainable architectures. Mechanochemical synthesis offers a promising yet largely unexplored route to supramolecular organic frameworks (SOFs), with the potential to fine-tune their topology and properties through a green and efficient process. • Supramolecular Organic Frameworks are flexible, tuneable porous materials. • Mechanosynthesis is a green, versatile strategy for synthesising SOFs. • The review covers the path of supramolecular mechanochemistry. • The mechanosynthesis of HOFs and XOFs is presented.