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The realization of a pair of photoreactive polymorphic co-crystals that are held together by the combination of I⋯N halogen bonding interactions and C–H⋯Cl contacts is reported. The reactant molecule within these co-crystals is based upon an unsymmetrical olefin, namely 4-stilbazole, that results in a regioselective solid-state [2 + 2] cycloaddition reaction in both polymorphic forms. Each solid undergoes a quantitative photoreaction which yields exclusively the head-to-tail photoproduct.more » « less
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