Template-Directed In Crystallo Photopolymerization of a Donor–Acceptor Cyclopropane: When Everything Falls into Place! - MédiHAL Access content directly
Image Year : 2024

Template-Directed In Crystallo Photopolymerization of a Donor–Acceptor Cyclopropane: When Everything Falls into Place!

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”.

Dates and versions

hal-04617162 , version 1 (19-06-2024)

Licence

Public Domain

Identifiers

  • HAL Id : hal-04617162 , version 1

Cite

Michel Giorgi, Kévin Masson, Sara Chentouf, Laurent Commeiras, Paola Nava, et al.. Template-Directed In Crystallo Photopolymerization of a Donor–Acceptor Cyclopropane: When Everything Falls into Place!. France. 2024. ⟨hal-04617162⟩

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