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Inorganic Carcerand: Kinetically Persistent Confinement Through Asymmetric Gating.

Akari Nakashuku1, Chinatsu Murata1, Jaeseob Shin1

  • 1Graduate School of Environmental Science, Hokkaido University, Sapporo, Japan.

Chemistry (Weinheim an Der Bergstrasse, Germany)
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We developed persistent molecular confinement using {Mo132} polyoxometalate cages. These inorganic carcerands trap bulky organic molecules, preventing release via asymmetric gating for stable encapsulation.

Keywords:
cluster compoundscontainer complexhost–guest systemspolyoxometalates

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Area of Science:

  • Supramolecular Chemistry
  • Materials Science
  • Nanotechnology

Background:

  • Molecular encapsulation is crucial for controlled release and stabilization.
  • Developing cages with selective guest uptake and retention remains a challenge.
  • Polyoxometalates offer unique structures for host-guest chemistry.

Purpose of the Study:

  • To introduce and demonstrate persistent molecular confinement.
  • To utilize a Keplerate-type polyoxometalate ({Mo132}) as an inorganic carcerand.
  • To investigate the mechanism of guest encapsulation and release.

Main Methods:

  • Synthesis and characterization of the {Mo132} polyoxometalate.
  • Guest screening experiments with various organic molecules.
  • Thermal and mechanochemical activation for guest entry.
  • Kinetic analysis of guest release.

Main Results:

  • The {Mo132} cage successfully confined bulky polar organic molecules.
  • Guest entry was facilitated by dipole-driven interactions, excluding nonpolar guests.
  • Encapsulated guests showed persistent retention, indicating irreversible uptake.
  • Asymmetric gating, not strong binding, governs the release kinetics.

Conclusions:

  • Persistent molecular confinement is achievable through kinetically enforced encapsulation.
  • Asymmetric gating provides a principle for designing cages with controlled guest retention.
  • {Mo132} polyoxometalates serve as effective inorganic carcerands for bulky guest molecules.