Dhaka Arun, Jeon Ie-Rang, Jeannin Olivier, Aubert Emmanuel, Espinosa Enrique, Fourmigué Marc
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226, 35042, Rennes, France.
Laboratoire CRM2, UMR CNRS 7036, Institut Jean Barriol, Université de Lorraine, BP 70239, 54506, Vandoeuvre-les-Nancy, France.
Angew Chem Int Ed Engl. 2022 Mar 1;61(10):e202116650. doi: 10.1002/anie.202116650. Epub 2022 Jan 20.
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 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.
