Modulation of porosity in a solid material enabled by bulk photoisomerization of an overcrowded alkene


The incorporation of photoswitchable molecules into solid-state materials holds promise for the fabrication of responsive materials, the properties of which can be controlled on-demand. However, the possible applications of these materials are limited due to the restrictions imposed by the solid-state environment on the incorporated photoswitches, which render the photoisomerization inefficient. Here we present responsive porous switchable framework materials based on a bistable chiroptical overcrowded alkene incorporated in the backbone of a rigid aromatic framework. As a consequence of the high intrinsic porosity, the resulting framework readily responds to a light stimulus, as demonstrated by solid-state Raman and reflectance spectroscopies. Solid-state 13C NMR spectroscopy highlights an efficient and quantitative bulk photoisomerization of the incorporated light-responsive overcrowded olefins in the solid material. Taking advantage of the quantitative photoisomerization, the porosity of the framework and the consequent gas adsorption can be reversibly modulated in response to light and heat.

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Fig. 1: Photoisomerization of the overcrowded olefin-based bistable switch.
Fig. 2: Synthesis, structure, sorption and thermal properties of PSF materials.
Fig. 3: Photochemical isomerization of bistable switch 1-Br2 in solution.
Fig. 4: Photochemical isomerization studies in the solid state.
Fig. 5: Solid-state NMR observations of the reversible structural switching in PSF-2.
Fig. 6: Switching of the gas adsorption properties.

Data availability

The data associated with the reported findings are available in the manuscript or the Supplementary Information. Other related data are available from the corresponding author upon request.


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This work was supported financially by the Netherlands Organization for Scientific Research (NWO-CW), the European Research Council (ERC, advanced grant no. 694345 to B.L.F.), the Ministry of Education, Culture and Science (Gravitation Program no. 024.001.035). We thank the University of Groningen for access to the Peregrine Computing Cluster. A.C. and P.S. acknowledge Ministero dell’Istruzione, dell’Università e della Ricerca (MIUR—Progetto Dipartimento di Eccellenza 2018-2022), PRIN 2015CTEBBA and PRIN 20173L7W8K (NEMO) for financial support. We thank C. X. Bezuidenhout for conformational analysis.

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W.D., F.C., S.J.W., P.S. and B.L.F. conceived the project. W.D. synthesized the bistable switch 1-Br2 and F.C. synthesized the PSF materials. W.D. performed photoisomerization studies in solution, and Raman and DR UV-vis studies of the PSFs. J.P. performed gas adsorption isotherms and the evaluation of adsorption energy. S.B. and A.C. performed solid-state NMR studies on the synthesized materials. F.C. performed differential scanning calorimetry, thermogravimetric analysis and gas-uptake experiments. W.D. performed DFT studies. S.J.W., A.C. and B.L.F. guided the project. W.D., A.C., S.J.W., P.S. and B.L.F. wrote the manuscript. All the authors discussed the results and commented on the manuscript.

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Correspondence to Sander J. Wezenberg or Angiolina Comotti or Ben L. Feringa.

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Supplementary information

Supplementary Information

Additional information on chemicals, structures and synthetic schemes, further NMR studies on isomerization in solution, additional solid-state NMR data on PSF-1 and PSF-2, additional N2 and CO2 adsorption isotherms of the PSFs and computational details.

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Castiglioni, F., Danowski, W., Perego, J. et al. Modulation of porosity in a solid material enabled by bulk photoisomerization of an overcrowded alkene. Nat. Chem. 12, 595–602 (2020).

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