Abstract
AbstractRegiochemistry of topochemical reactions depends on the crystal packing and biasing the regiochemistry necessitates precise crystal engineering. The pristine crystals of monomer 1 upon topochemical azide‐alkyne cycloaddition (TAAC) reaction give a 1 : 1 blend of 1,4‐ and 1,5‐triazole‐linked polymers due to the presence of two self‐sorted reactive conformers in the crystal. We designed a binary isomorphous cocrystal of monomer 1 and a structurally similar dummy molecule 2 to limit the number of reactive conformers of 1 to one and thus to get one type of polymer. Equimolar solution of 1 and 2 in chloroform‐acetone mixture gave two 1 : 1 cocrystals Co‐I and Co‐II. The Co‐II, a chloroform adduct, on heating undergoes desolvation and polymorphic transition to Co‐I. Co‐I is isomorphic to 1 and 2 and possess self‐sorted arrays of 1 and 2. Heating Co‐I results in the TAAC polymerization giving 1,4‐triazolyl‐linked polymer of 1 selectively, showing the power of crystal engineering in regiocontrol.
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