Playing with Isomerism: Cocrystallization of Isomeric N-Salicylideneaminopyridines with Perfluorinated Compounds as Halogen Bond Donors and Its Impact on Photochromism

Andréa Carletta, Marija Zbačnik, Mégane Van Gysel, Matea Vitković, Nikolay Tumanov, Vladimir Stilinović, Johan Wouters, Dominik Cinčić

Research output: Contribution to journalArticlepeer-review

Abstract

In N-salicylideneaniline derivatives, photochromism occurs by a two-step isomerization mechanism. Photochromism has been reported to be closely related to the molecular conformation of the N-salicylideneanilines (described by the dihedral angle Φ) and to the free available space (Vfree) in the crystal. In this contribution, we focus on cocrystals of isomeric N-salicylideneaminopyridines with perfluorinated halogen bond donors as coformers. The advantage of working with isomers is that they have a similar (if not equal) molecular volume. This aspect means that the evaluation and comparison of the free available spaces within cocrystals is not affected by the differences in the molecular volumes of their constituents. Cocrystals were synthesized by a one-pot procedure, which allowed concomitant formation of covalent (imine) and noncovalent (halogen) bonds. Each cocrystal was characterized by X-ray diffraction, and its photochromism was assessed by UV−vis diffuse reflectance. Our results suggest that the Φ/Vfree model grossly oversimplifies the complexity of the dynamic phenomenon behind the photoisomerization of N-salicylideneanilines. For the above-mentioned reasons, careful examination of intermolecular interactions and crystals packing (localization of voids, evaluation of intermolecular interactions and stacking modes) should be taken into account and used to supplement the current proposed model based on Φ and Vfree.
Original languageEnglish
Pages (from-to)6833–6842
Number of pages10
JournalCrystal Growth and Design
Volume18
Issue number11
Early online date12 Sep 2018
DOIs
Publication statusPublished - 7 Nov 2018

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