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Published on: August 10, 2017
Topochemical Polymerization of a Diacetylene in a Chalcogen-Bonded (ChB) Assembly
Arun Dhaka1, Ie-Rang Jeon1, Olivier Jeannin1
1Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226, 35042, Rennes, France.
Abstract:
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⋅⋅⋅NPy 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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