Reversible switching of arylazopyrazole within a metal-organic cage

Anton I. Hanopolskyi, Soumen De, Michał J. Białek, Yael Diskin-Posner, Liat Avram, Moran Feller, Rafal Klajn

Research output: Contribution to journalArticle

Abstract

Arylazopyrazoles represent a new family of molecular photoswitches characterized by a near-quantitative conversion between two states and long thermal half-lives of the metastable state. Here, we investigated the behavior of a model arylazopyrazole in the presence of a self-assembled cage based on Pd-imidazole coordination. Owing to its high water solubility, the cage can solubilize the E isomer of arylazopyrazole, which, by itself, is not soluble in water. NMR spectroscopy and X-ray crystallography have independently demonstrated that each cage can encapsulate two molecules of E-arylazopyrazole. UV-induced switching to the Z isomer was accompanied by the release of one of the two guests from the cage and the formation of a 1:1 cage/Z-arylazopyrazole inclusion complex. DFT calculations suggest that this process involves a dramatic change in the conformation of the cage. Back-isomerization was induced with green light and resulted in the initial 1:2 cage/E-arylazopyrazole complex. This back-isomerization reaction also proceeded in the dark, with a rate significantly higher than in the absence of the cage.

Original languageEnglish
Pages (from-to)2398-2407
Number of pages10
JournalBeilstein Journal of Organic Chemistry
Volume15
DOIs
Publication statusPublished - Oct 10 2019

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Isomerization
Isomers
Metals
Methyl Green
Water
X ray crystallography
Discrete Fourier transforms
Nuclear magnetic resonance spectroscopy
Conformations
Solubility
Molecules
Hot Temperature
imidazole

Keywords

  • Arylazopyrazoles
  • Coordination cages
  • Inclusion complexes
  • Molecular switches
  • Photochromism

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Hanopolskyi, A. I., De, S., Białek, M. J., Diskin-Posner, Y., Avram, L., Feller, M., & Klajn, R. (2019). Reversible switching of arylazopyrazole within a metal-organic cage. Beilstein Journal of Organic Chemistry, 15, 2398-2407. https://doi.org/10.3762/bjoc.15.232

Reversible switching of arylazopyrazole within a metal-organic cage. / Hanopolskyi, Anton I.; De, Soumen; Białek, Michał J.; Diskin-Posner, Yael; Avram, Liat; Feller, Moran; Klajn, Rafal.

In: Beilstein Journal of Organic Chemistry, Vol. 15, 10.10.2019, p. 2398-2407.

Research output: Contribution to journalArticle

Hanopolskyi, AI, De, S, Białek, MJ, Diskin-Posner, Y, Avram, L, Feller, M & Klajn, R 2019, 'Reversible switching of arylazopyrazole within a metal-organic cage', Beilstein Journal of Organic Chemistry, vol. 15, pp. 2398-2407. https://doi.org/10.3762/bjoc.15.232
Hanopolskyi AI, De S, Białek MJ, Diskin-Posner Y, Avram L, Feller M et al. Reversible switching of arylazopyrazole within a metal-organic cage. Beilstein Journal of Organic Chemistry. 2019 Oct 10;15:2398-2407. https://doi.org/10.3762/bjoc.15.232
Hanopolskyi, Anton I. ; De, Soumen ; Białek, Michał J. ; Diskin-Posner, Yael ; Avram, Liat ; Feller, Moran ; Klajn, Rafal. / Reversible switching of arylazopyrazole within a metal-organic cage. In: Beilstein Journal of Organic Chemistry. 2019 ; Vol. 15. pp. 2398-2407.
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