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Updated: May 12, 2026

Performing In Situ Closed-Cell Gas Reactions in the Transmission Electron Microscope
Published on: July 24, 2021
Chemistry inside molecular containers in the gas phase
Tung-Chun Lee1, Elina Kalenius, Alexandra I Lazar
1Melville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK.
Gas-phase reactions within cucurbituril hosts reveal how host-guest interactions control chemical transformations. This supramolecular chemistry insight is key for understanding catalysis and molecular recognition.
Area of Science:
- Supramolecular Chemistry
- Physical Organic Chemistry
- Chemical Physics
Background:
- Inner-phase chemical reactions in host cavities offer insights into transition state stabilization, mimicking enzyme active sites.
- While known in solution, gas-phase studies of these reactions are challenging due to host-guest complex dissociation.
Purpose of the Study:
- To systematically investigate gas-phase inner-phase chemical reactions using cucurbiturils and bicyclic azoalkanes.
- To understand the interplay of host-guest interactions governing reactivity within supramolecular assemblies.
Main Methods:
- Utilized mass spectrometry for gas-phase investigation of host-guest systems.
- Employed cucurbiturils as macrocyclic hosts and bicyclic azoalkanes as guests.
- Analyzed the balance between attractive/repulsive van der Waals forces and constrictive binding.
Main Results:
- Demonstrated that thermally activated reactions can compete with dissociation in gas-phase supramolecular assemblies.
- Identified a sensitive interplay of attractive and repulsive van der Waals forces and binding constrictivity.
- Showcased the ability to control reactivity through host-guest size complementarity.
Conclusions:
- Gas-phase inner-phase reactions are feasible and controllable within cucurbituril hosts.
- Understanding host-guest interactions is crucial for designing reactive supramolecular systems.
- These findings have significant implications for supramolecular reactivity and catalysis.
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