The organic solid state is an intriguing medium to form molecules. In principle, molecules that are less accessible or completely unavailable in solution can be constructed in the solid state. To achieve reactivity in solids, it is critical that reactive centers are assembled and oriented in a proper geometry to react. Problems of crystal packing, and particularly as related to polymorphism, can thwart efforts of chemists to rationally design solids with prescribed reactivity. In this presentation, we describe a general approach to control the formation of covalent bonds in molecular crystals. Hydrogen bonds, coordination bonds, and halogen bonds are used to direct intermolecular [2+2] photodimerizations as a way to utilize principles of supramolecular chemistry to construct molecules. Constructions of complex target molecules such as [n]ladderanes and [2.2]cyclophanes are achieved stereoselectively and in quantitative yield via molecular cocrystals. Our recent efforts to expand the method to B-N bonds and facilitiate phototriggered release of guest molecules will also be described.

Solid-state reactivity, cocrystals, and polymorphism: Connecting the dots to construct molecules in solids

ACS Spring Meeting 2021

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