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Racemic and enantiopure phenylalanine sulfonamides preferentially crystallize to give supramolecular dimers with favorable olefin⋯olefin spacing (3.77–4.01 Å) for programmed solid-state [2 + 2] photodimerizations.

Graphical abstract: Solid-state photodimerization reactions of racemic and homochiral phenylalanine sulfonamidecinnamic acids

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