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

Fingerprint

Halogens
Crystals
Photochromism
Imines
Crystalline materials
Derivatives
Bromine
Condensation reactions
Emission spectroscopy
Crystallization
Iodine
Absorption spectroscopy
Ultraviolet radiation
Nuclear magnetic resonance spectroscopy
Solid solutions
X ray diffraction

Keywords

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

Cite this

Carletta, A., Spinelli, F., d'Agostino, S., Ventura, B., Chierotti, M. R., Gobetto, R., ... Grepioni, F. (2017). Halogen-Bond Effects on the Thermo- and Photochromic Behaviour of Anil-Based Molecular Co-crystals. Chemistry - A European Journal, 23(22), 5317-5329. https://doi.org/10.1002/chem.201605953
Carletta, Andrea ; Spinelli, Floriana ; d'Agostino, Simone ; Ventura, Barbara ; Chierotti, Michele R ; Gobetto, Roberto ; Wouters, Johan ; Grepioni, Fabrizia. / Halogen-Bond Effects on the Thermo- and Photochromic Behaviour of Anil-Based Molecular Co-crystals. In: Chemistry - A European Journal. 2017 ; Vol. 23, No. 22. pp. 5317-5329.
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Carletta, A, Spinelli, F, d'Agostino, S, Ventura, B, Chierotti, MR, Gobetto, R, Wouters, J & Grepioni, F 2017, 'Halogen-Bond Effects on the Thermo- and Photochromic Behaviour of Anil-Based Molecular Co-crystals', Chemistry - A European Journal, vol. 23, no. 22, pp. 5317-5329. https://doi.org/10.1002/chem.201605953

Halogen-Bond Effects on the Thermo- and Photochromic Behaviour of Anil-Based Molecular Co-crystals. / Carletta, Andrea; Spinelli, Floriana; d'Agostino, Simone; Ventura, Barbara; Chierotti, Michele R; Gobetto, Roberto; Wouters, Johan; Grepioni, Fabrizia.

In: Chemistry - A European Journal, Vol. 23, No. 22, 2017, p. 5317-5329.

Research output: Contribution to journalArticle

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AU - Carletta, Andrea

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AU - d'Agostino, Simone

AU - Ventura, Barbara

AU - Chierotti, Michele R

AU - Gobetto, Roberto

AU - Wouters, Johan

AU - Grepioni, Fabrizia

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