The ability to reliably form covalent bonds in organic crystalline solids promises to provide access to product molecules that may be completely unavailable to chemists in solution. Critical covalent bonding forming process occur in solids without use of solvent and with the materials being accesible using mechanochemistry. Crystal packing, however, is a nemesis of the crystal engineer since covalent bond formations generally require reactive sites to be deliberately assembled and oriented in close proximity to react. In this presentation, we describe a method to direct the formation of covalent bonds in crystals using principles of supramolecular chemistry. A main reaction of focus is the [2+2] photodimerization. The method relies on the use of small molecules, coordination complexes, and metal-organic frameworks as templates to assemble olefins via supramolecular synthons into geometries for inter- and intramolecular cycloadditions. The method enables the synthesis of complex molecules such as [2.2]cyclophanes and [<i>n</i>]-ladderanes with emerging properties (e.g. ligands in coordination chemistry). Relevance of the work to pharmaceutics and energy capture and release will also be discussed.

Building molecules in crystals: Green chemistry to sustainable materials research

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ACS Spring 2023

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