Speed Tuning of the Formation/Dissociation of a Metallorotaxane

  • Yoko Sakata
    Graduate School of Natural Science and Technology Kanazawa University Kakuma-machi Kanazawa 920-1192 Japan
  • Ryosuke Nakamura
    Graduate School of Natural Science and Technology Kanazawa University Kakuma-machi Kanazawa 920-1192 Japan
  • Toshihiro Hibi
    Graduate School of Natural Science and Technology Kanazawa University Kakuma-machi Kanazawa 920-1192 Japan
  • Shigehisa Akine
    Graduate School of Natural Science and Technology Kanazawa University Kakuma-machi Kanazawa 920-1192 Japan

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<jats:title>Abstract</jats:title><jats:p>Switching between the formation/dissociation of rotaxanes is important to control the function of various types of rotaxane‐based materials. We have developed a convenient and simple strategy, the so‐called “accelerator addition”, to make a static rotaxane dynamic without apparently affecting the chemical structure. As an interlocked molecule that enables tuning of the formation/dissociation speed, a metallorotaxane was quantitatively generated by the complexation of a triptycene‐based dumbbell‐shaped mononuclear complex, [PdL<jats:sub>2</jats:sub>]<jats:sup>2+</jats:sup> (L=2,3‐diaminotriptycene), with 27C9. As a result of the inertness of the Pd<jats:sup>2+</jats:sup>‐based coordination structure, the metallorotaxane was slowly formed (the static state). This rotaxane formation was accelerated 27 times simply by adding Br<jats:sup>−</jats:sup> as an accelerator (the dynamic state). A similar drastic acceleration was also demonstrated during the dissociation process when Cs<jats:sup>+</jats:sup> was added to the metallorotaxane to form the free axle [PdL<jats:sub>2</jats:sub>]<jats:sup>2+</jats:sup> and the 27C9‐Cs<jats:sup>+</jats:sup> complex.</jats:p>

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