A Syndiotactic Polymer via Spontaneous Exoselective Single-Crystal-To-Single-Crystal Topochemical Diels-Alder
Sourav Pathak1, Kana M Sureshan1
1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Thiruvananthapuram, Kerala 695551, India.
Abstract:
We designed and synthesized an amide-based monomer decorated with furan as the diene unit and maleimide as the dienophile unit at its termini. Single-crystal X-ray diffraction (SCXRD) analysis of its crystal revealed a head-to-tail arrangement of molecules with furan and maleimide groups of neighboring molecules proximally placed in an arrangement suitable for their topochemical Diels-Alder cycloaddition (TDAC) to form a linear polymer. The monomer underwent a spontaneous single-crystal-to-single-crystal (SCSC) polymerization at room temperature, yielding a linear polymer with oxa-bicyclic linkage. SCXRD analysis revealed that the cycloaddition occurred in an exoselective manner, and the absolute stereochemistry of the oxa-bicyclic linkage alternated in successive repeat units, leading to a syndiotactic linear polymer. The polymerization can be accelerated by heating the powder at 120 °C; the topochemical nature of the high-temperature reaction was established by time dependent differential scanning calorimetry (DSC), time-dependent powder X-ray diffraction (PXRD), and UV-visible spectroscopic analysis; the polymer was characterized using solid-state NMR spectroscopy and MALDI-TOF mass spectrometry.
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