Dynamic Metalloporphyrin‐Based [2]Rotaxane Molecular Shuttles Stimulated by Neutral Lewis Base and Anion Coordination

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Abstract
A series of dynamic metalloporphyrin [2]rotaxane molecular shuttles comprising of bis‐functionalised Zn(II) porphyrin axle and pyridyl functionalised macrocycle components are prepared in high yield via active metal template synthetic methodology. Extensive variable temperature 1H NMR and quantitative UV‐Vis spectroscopic titration studies demonstrate dynamic macrocycle translocation is governed by an inter‐component co‐ordination interaction between the macrocycle pyridyl and axle Zn(II) metalloporphyrin, which serves to bias a ‘resting state’ co‐conformation. The dynamic shuttling behaviour of the interlocked structures is dramatically inhibited by the addition of a neutral Lewis base such as pyridine, but can also be tuned via post‐synthetic rotaxane demetallation of the porphyrin axle core to give free‐base, or upon subsequent metallation, Ni(II) [2]rotaxane analogues. Importantly, the Lewis acidic Zn(II) porphyrin axle component is also capable of coordinating anions which induces mechanical bond shuttling behaviour resulting in a novel optical sensing response.
Funding Information
  • Engineering and Physical Sciences Research Council (EP/S023828/1, EP/N509711/1)

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