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Updated: Jun 24, 2025

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
Template-Directed In Crystallo Photopolymerization of a Donor-Acceptor Cyclopropane: When Everything Falls into
Michel Giorgi1, Kévin Masson2, Sara Chentouf1
1Aix Marseille Universite, CNRS, Centrale Méditerranée, FSCM, 13397 Marseille, France.
Abstract:
A single-crystal-to-single-crystal solid-state reaction of vinylogous donor-acceptor cyclopropanes is documented. The enantiospecific synthesis of new products, distinct from those obtained in solution, is achieved for the target compounds. Photopolymerization occurred upon X-ray exposure to the crystals. Notably, in one case, this reactivity exhibits selectivity since an ordered arrangement of polymers and unreacted cocrystallized monomeric conformers has been observed. Structural characterization of the complete transformation monitored through single-crystal X-ray diffraction and supported by molecular dynamics simulations sheds light on the subtle role of crystal packing in the reaction process. Moreover, the X-ray diffraction (XRD)-resolved structure of a donor-acceptor cyclopropane intermediate reveals an elongation in bond length that corroborates the existence of the so-called "push-pull effect".
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