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 journalArticle

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

Fingerprint

Photochromism
photochromism
Halogens
halogens
Photoisomerization
Crystals
Imines
evaluation
supplements
Dihedral angle
Isomerization
Isomers
imines
isomerization
crystals
Conformations
dihedral angle
voids
isomers
examination

Cite this

@article{c3952301ed404cd8856c4728b9b55df5,
title = "Playing with Isomerism: Cocrystallization of Isomeric N-Salicylideneaminopyridines with Perfluorinated Compounds as Halogen Bond Donors and Its Impact on Photochromism",
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.",
author = "Andr{\'e}a Carletta and Marija Zbačnik and {Van Gysel}, M{\'e}gane and Matea Vitković and Nikolay Tumanov and Vladimir Stilinović and Johan Wouters and Dominik Cinčić",
year = "2018",
month = "11",
day = "7",
doi = "10.1021/acs.cgd.8b01064",
language = "English",
volume = "18",
pages = "6833–6842",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",
number = "11",

}

Playing with Isomerism : Cocrystallization of Isomeric N-Salicylideneaminopyridines with Perfluorinated Compounds as Halogen Bond Donors and Its Impact on Photochromism. / Carletta, Andréa; Zbačnik, Marija; Van Gysel, Mégane; Vitković, Matea; Tumanov, Nikolay; Stilinović, Vladimir; Wouters, Johan; Cinčić, Dominik.

In: Crystal Growth and Design, Vol. 18, No. 11, 07.11.2018, p. 6833–6842.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Playing with Isomerism

T2 - Cocrystallization of Isomeric N-Salicylideneaminopyridines with Perfluorinated Compounds as Halogen Bond Donors and Its Impact on Photochromism

AU - Carletta, Andréa

AU - Zbačnik, Marija

AU - Van Gysel, Mégane

AU - Vitković, Matea

AU - Tumanov, Nikolay

AU - Stilinović, Vladimir

AU - Wouters, Johan

AU - Cinčić, Dominik

PY - 2018/11/7

Y1 - 2018/11/7

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85054212428&partnerID=8YFLogxK

U2 - 10.1021/acs.cgd.8b01064

DO - 10.1021/acs.cgd.8b01064

M3 - Article

VL - 18

SP - 6833

EP - 6842

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 11

ER -