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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)
|June 7, 2026
Summary
We developed persistent molecular confinement using {Mo132} polyoxometalate cages. These inorganic carcerands trap bulky organic molecules, preventing release via asymmetric gating for stable encapsulation.
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.
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