Halogen-Bond Effects on the Thermo- and Photochromic Behaviour of Anil-Based Molecular Co-crystals

Andrea Carletta, Floriana Spinelli, Simone d'Agostino, Barbara Ventura, Michele R Chierotti, Roberto Gobetto, Johan Wouters, Fabrizia Grepioni

Research output: Contribution to journalArticle

Abstract

N-Salicilideneanilines are among the most studied thermo- and photochromic systems in the solid state. Although thermochromism is a general property of crystalline N-salicilideneanilines, photochromism is known in a limited number of cases. As a method for the construction of thermo- and photo-responsive molecular architectures, the co-crystallisation of 1,2,4,5-tetrafluoro-3,6-diiodobenzene (I2F4) with three selected imines of o-vanillin, named 1, 2 and 3, obtained through a condensation reaction with 3-aminopyridine, 4-bromoaniline and 4-iodoaniline, respectively, is reported herein. All crystals and co-crystals have been characterised by means of solid-state complementary techniques (X-ray diffraction, solid-state NMR spectroscopy, absorption and emission spectroscopy). The role of halogen bonding and crystal packing in the optical and chromic properties of all solid materials is discussed. All solids exhibit thermochromic behaviour, and three of them (2, 22 ⋅I2F4 and 32 ⋅I2F4) are also photochromic. Imine derivative 3 crystallises in two different polymorphic forms (3 A and 3 B) and a solvate (3Solv ). The bromo and iodo derivatives, 2 and 3 B, are isomorphous and form isomorphous co-crystals with I2F4, but behave differently when exposed to UV light because only crystalline 2 is photochromic. Interestingly, the replacement of bromine with iodine seems to turn off the photochromism because crystalline 3 A and 3Solv , and even the 20.7 30.3 solid solution, do not manifest photochromic behaviour.

Original languageEnglish
Pages (from-to)5317-5329
Number of pages13
JournalChemistry - A European Journal
Volume23
Issue number22
DOIs
Publication statusPublished - 2017

Keywords

  • Journal Article
  • photochromism
  • thermochromism
  • halogen bonds
  • NMR spectroscopy
  • solid-state reactions

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  • Datasets

    CCDC 1483225: Experimental Crystal Structure Determination

    CARLETTA, A. (Contributor), Chierotti, M. R. (Contributor), d'Agostino, S. (Contributor), Gobetto, R. (Contributor), Grepioni, F. (Contributor), Spinelli, F. (Contributor), Ventura, B. (Contributor) & WOUTERS, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017

    Dataset

    CCDC 1483227: Experimental Crystal Structure Determination

    CARLETTA, A. (Contributor), Chierotti, M. R. (Contributor), d'Agostino, S. (Contributor), Gobetto, R. (Contributor), Grepioni, F. (Contributor), Spinelli, F. (Contributor), Ventura, B. (Contributor) & WOUTERS, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017

    Dataset

    CCDC 1483232: Experimental Crystal Structure Determination

    CARLETTA, A. (Contributor), Chierotti, M. R. (Contributor), d'Agostino, S. (Contributor), Gobetto, R. (Contributor), Grepioni, F. (Contributor), Spinelli, F. (Contributor), Ventura, B. (Contributor) & WOUTERS, J. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017

    Dataset

    Student Theses

    Photochromic multicomponent crystalline materials based on N-salicylideneanilines

    Author: Carletta, A., 13 Sep 2019

    Supervisor: Wouters, J. (Supervisor), Leherte, L. (President), Champagne, B. (Jury), Leyssens, T. (External person) (Jury) & Roscini, C. (External person) (Jury)

    Student thesis: Doc typesDoctor of Sciences

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