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The successful topochemical polymerization of bis(selenocyanatomethyl)butadyine 1 is achieved upon association in a 1 : 1 co‐crystal with 1,2‐bis(2‐pyridyl)ethylene (2‐bpen) through strong and linear (NC) − Se⋅⋅⋅N Py chalcogen bonding (ChB) interactions, allowing for an appropriate parallel alignment of the diacetylene moieties toward the solid‐state reaction. Co‐crystal 1 ⋅(2‐bpen) undergoes polymerization upon heating at 100 °C. The reaction progress was monitored by IR, DSC and PXRD. An enhancement of the polymer conductivity by 8 orders of magnitude is observed upon iodine doping. Strikingly, the course of polymerization is accompanied with sublimation of the ChB acceptor molecules 2‐bpen, providing the polymer in a pure form with full recovery of the co‐former, at variance with the usual hydrogen‐bonded co‐crystal strategies toward polydiacetylenes .
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Dhaka et al. (2022) studied this question.
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