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Photoactivation of a nanoporous crystal for on-demand guest trapping and conversion

Nature Materials volume 9, pages 661–666 (2010)Cite this article

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Abstract

Porous compounds are ubiquitous and indispensable in daily life as adsorbents and catalysts. The discovery of a new porous compound with unique properties based on intrinsic nanosized space and surface functionalities is scientifically and technologically important. However, the functional species used in this context are limited to those that are sufficiently inert to not spoil the porous structures. Here, we show a new strategy to achieve a crystalline porous material with the pore surface regularly decorated with highly reactive ‘bare’ nitrenes that are photonically generated from stable ‘dormant’ precursors at will. The bare triplet nitrenes were accessible to and reacted with adsorbed oxygen or carbon monoxide molecules, which showed not only activation of the pore surface, but also a high probability of chemical trapping and conversion of guest molecules by light stimulation on demand.

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Figure 1: Schematic illustration of photoactivation of a PCP with azide functionalities.
Figure 2: X-ray crystal structural analyses.
Figure 3: Photochemical reactions of CID-N3 monitored by infrared measurements.
Figure 4: 1H-NMR study of the photochemical products from dried CID-N3.
Figure 5: In situ photoactivation of CID-N3 with adsorption of oxygen.

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Acknowledgements

The synchrotron radiation experiments were carried out at BL02B1 in SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal no. 2009A1569).

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Authors and Affiliations

  1. Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology Agency (JST), Kyoto 600-8815, Japan

    Hiroshi Sato, Ryotaro Matsuda & Susumu Kitagawa

  2. Institute for Integrated Cell-Material Sciences, Kyoto University, Kyoto 615-8510, Japan

    Ryotaro Matsuda & Susumu Kitagawa

  3. Japan Synchrotron Radiation Research Institute/SPring-8, Hyogo 679-5198, Japan

    Kunihisa Sugimoto & Masaki Takata

  4. Department of Advanced Materials Science, The University of Tokyo, Chiba 277-8561, Japan

    Masaki Takata

  5. RIKEN SPring-8 Center, Hyogo 679-5148, Japan

    Masaki Takata & Susumu Kitagawa

  6. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615–8510, Japan

    Susumu Kitagawa

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  1. Hiroshi Sato
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Contributions

H.S., R.M. and S.K. conceived the project. H.S. and R.M. prepared and analysed all compounds described and carried out the sorption, spectroscopic measurements and photochemical experiments. K.S. and M.T. assisted the crystallographic study using synchrotron X-rays. H.S., R.M. and S.K. designed the study, analysed the data and wrote the paper.

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Correspondence to Ryotaro Matsuda or Susumu Kitagawa.

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The authors declare no competing financial interests.

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Sato, H., Matsuda, R., Sugimoto, K. et al. Photoactivation of a nanoporous crystal for on-demand guest trapping and conversion. Nature Mater 9, 661–666 (2010). https://doi.org/10.1038/nmat2808

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