Stabilization of radical active species in a MOF nanospace to exploit unique reaction pathways

Yuki Harada; Shinpei Kusaka; Toshinobu Nakajo; Jun Kumagai; Cho Rong Kim; Joo Young Shim; Akihiro Hori; Yunsheng Ma; Ryotaro Matsuda

doi:10.1039/D1CC04267J

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Stabilization of radical active species in a MOF nanospace to exploit unique reaction pathways†

Yuki Harada,

^a Shinpei Kusaka,

^a Toshinobu Nakajo,

^a Jun Kumagai,

^b Cho Rong Kim,

^a Joo Young Shim,^a Akihiro Hori,

^a Yunsheng Ma

^ac and Ryotaro Matsuda

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry and Biotechnology, School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
E-mail: ryotaro.matsuda@chembio.nagoya-u.ac.jp

^b Institute of Materials and Systems for Sustainability, Division of Materials Research, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan

^c School of Chemistry and Materials Engineering, Jiangsu Key Laboratory of Advanced Functional Materials, Changshu Institute of Technology, Changshu, Jiangsu 215500, P. R. China

Abstract

We synthesized a metal–organic framework (MOF) using a ligand bearing haloalkoxy chains as a radical precursor. The radicals generated in the MOF upon photoirradiation were stable even at 250 K or under an O₂ atmosphere, despite radicals generated from the ligand decomposing at 200 K; thus, the regular arrangement of radicals effectively stabilized them. Moreover, a unique photoproduct was obtained only in the MOF, indicating that the confinement effect in the nanospace enabled a specific reaction that did not occur in the bulk state. We propose a new platform for exploring chemical reactions and materials based on reactive species.

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DOI: https://doi.org/10.1039/D1CC04267J
Article type: Communication
Submitted: 05 Aug 2021
Accepted: 14 Oct 2021
First published: 14 Oct 2021

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Chem. Commun., 2021,57, 12115-12118

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Stabilization of radical active species in a MOF nanospace to exploit unique reaction pathways

Y. Harada, S. Kusaka, T. Nakajo, J. Kumagai, C. R. Kim, J. Y. Shim, A. Hori, Y. Ma and R. Matsuda, Chem. Commun., 2021, 57, 12115 DOI: 10.1039/D1CC04267J

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Chemical Communications

Stabilization of radical active species in a MOF nanospace to exploit unique reaction pathways†

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Stabilization of radical active species in a MOF nanospace to exploit unique reaction pathways

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