Controlling reactions in crystalline solids provides new opportunities in synthetic chemistry and material science. Much effort has been devoted to using supramolecular interactions (e.g., hydrogen bonding, halogen bonding and metal coordination) to direct the formation of covalent bonds in photoactive solids. The strategy focuses on using auxiliary molecules to assemble reactants (i.e., olefins) in a suitable geometry for a [2+2] photodimerization. While remarkable progress have been made in the field during the past decade, additional studies are essential to expand the toolbox of non-covalent interactions and enable the design and synthesis of smart solid materials, especially, achieving single-crystal-to-single-crystal (SCSC) reactivity remains challenging.<br/>In this presentation, we will describe (1) the use of gold(I) coordination and aurophilic interactions to construct a photoreactive tetranuclear gold(I) macrocycle. The photoreaction proceeds via a rare SCSC transformation accompanied by expansion of the unit cell that generates ramps on the surfaces of the single crystals. (2) A salt cocrystal of 4-stilbazole that undergoes a cascade-like [2+2] photodimerization. The photoreaction is enabled by a combination of N+-H...N hydrogen bond and cation-π interactions in an SCSC transformation. Our work extends the toolbox of crystal engineering and provides reliable approaches to access cyclobutane derivatives in the solid-state.

Controlling reactions in crystals: Metal-organic assemblies and salt cocrystals

ACS Spring Meeting 2021

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