Photoinduced Bending of Single Crystals of a Linear Bis-Olefin via Water-Templated Solid-State [2+2] Photopolymerization Reaction

Chemistry. 2020 Jan 7;26(2):396-400. doi: 10.1002/chem.201904481. Epub 2019 Dec 5.

Abstract

The single crystals of two structural isomers of bis-olefinic molecules were shown to have contrasting properties in terms of their photoreactivity: one exhibits an excellent ability to form polymers, accompanied with bending of crystals upon irradiation, while the other is photostable. The photoreactive crystal is a first example in which [2+2] polymerization leads to bending of the crystals, with implications for the design of photoactuators. The hydrate formation ability of one of these molecular isomers promotes the solid-state reactivity in its crystal, as the H2 O molecules act as a template to bring the olefin molecules into the required arrangement for [2+2] polymerization. Further, the crystals of the polymer exhibited better flexibility and smoothed surfaces compared to those of the monomers. In addition, under UV-light the diene emits bluish violet light while the polymer emits green light, indicating that the luminescence property can be tuned through photoirradiation.

Keywords: photoactuators; photochemistry; photoinduced bending; solid-state [2+2] photopolymerization.