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Multi-Stimuli-Responsive Interconversion between Bowl- and Capsule-Shaped Self-Assembled Zinc(II) Complexes.

Kenichi Endo1, Hitoshi Ube1, Mitsuhiko Shionoya1

  • 1Department of Chemistry, Graduate School of Science , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku , Tokyo 113-0033 , Japan.

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|December 6, 2019
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Researchers developed novel metal-organic frameworks that can transform between bowl and capsule shapes in response to multiple stimuli like ligands, acids, bases, solvents, and guests.

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Area of Science:

  • Supramolecular Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Metal-organic architectures exhibit structural plasticity, enabling applications in responsive systems.
  • Existing stimuli-responsive systems typically react to a single trigger.
  • Multi-stimuli responsive interconversion in metal-organic structures is highly desirable but rarely achieved.

Purpose of the Study:

  • To report multi-stimuli-responsive interconversion between distinct self-assembled zinc(II) complexes.
  • To explore the design principles for versatile functional materials.

Main Methods:

  • Synthesis of porphyrin-based ligand L and zinc(II) ions.
  • Investigation of equilibrium formation between Zn4L3X6 (bowl-shaped) and Zn4L4 (capsule-shaped) complexes.
  • Induction of structural interconversion using exogenous ligands, Brønsted acid/base, solvents, and guest molecules.

Main Results:

  • Demonstrated reversible interconversion between bowl-shaped [ZnII4L3X6] and capsule-shaped [ZnII4L4] complexes.
  • Identified four distinct external stimuli (ligands, acid/base, solvents, guests) that trigger the structural transformation.
  • Detailed mechanistic insights into the interconversion process based on equilibrium species.

Conclusions:

  • Achieved multi-stimuli-responsive structural interconversion in self-assembled zinc(II) complexes.
  • The findings provide a foundation for designing versatile, multi-responsive supramolecular systems.
  • This work highlights the potential for complex molecular transformations in functional materials.