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Reversible switching of arylazopyrazole within a metal–organic cage

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

Beilstein J. Org. Chem. 2019, 15, 2398–2407. https://doi.org/10.3762/bjoc.15.232

Supporting Information

The Supporting Information features further experimental details, including synthesis and characterization of arylazopyrazole 1, characterization of inclusion complexes (E-1)₂ [Graphic 2] 2 and (Z-1)2, photoisomerization and thermal relaxation studies, and details on X-ray data collection and refinement. In addition, X-ray data for inclusion complex (E-1)₂2 and the energy-optimized structure for inclusion complex (Z-1)2 are given.

Supporting Information File 1: Further experimental details.
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Supporting Information File 2: X-ray data for inclusion complex (E-1)₂2.
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Supporting Information File 3: Energy-optimized structure for inclusion complex (Z-1)2.
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Reversible switching of arylazopyrazole within a metal–organic cage

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

Beilstein J. Org. Chem. 2019, 15, 2398–2407. https://doi.org/10.3762/bjoc.15.232

How to Cite

Hanopolskyi, A. I.; De, S.; Białek, M. J.; Diskin-Posner, Y.; Avram, L.; Feller, M.; Klajn, R. Beilstein J. Org. Chem. 2019, 15, 2398–2407. doi:10.3762/bjoc.15.232

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TY  - JOUR
A1  - Hanopolskyi, Anton I.
A1  - De, Soumen
A1  - Białek, Michał J.
A1  - Diskin-Posner, Yael
A1  - Avram, Liat
A1  - Feller, Moran
A1  - Klajn, Rafal
T1  - Reversible switching of arylazopyrazole within a metal–organic cage
JF  - Beilstein Journal of Organic Chemistry
PY  - 2019///
VL  - 15
SP  - 2398
EP  - 2407
SN  - 1860-5397
DO  - 10.3762/bjoc.15.232
PB  - Beilstein-Institut
JA  - Beilstein J. Org. Chem.
UR  - https://doi.org/10.3762/bjoc.15.232
KW  - arylazopyrazoles
KW  - coordination cages
KW  - inclusion complexes
KW  - molecular switches
KW  - photochromism
N2  - 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.
ER  -

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aromatic	the word “aromatic”
aromatic aldehyde	the word “aromatic” OR “aldehyde”
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“aromatic aldehyde”	the exact phrase “aromatic aldehyde”
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