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Related Experiment Video

Updated: May 21, 2025

Design, Synthesis, and Photochemical Properties of Clickable Caged Compounds

Design, Synthesis, and Photochemical Properties of Clickable Caged Compounds

Published on: October 15, 2019

Kinetic Trapping of Rylene Diimide Covalent Organic Cages.

Sergey Fisher¹, Hsin-Hua Huang², Luise Sokoliuk²

¹Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, XH Amsterdam NL-1098, the Netherlands.

The Journal of Organic Chemistry

|March 18, 2025

Summary

Kinetically trapped imine cages were formed using dynamic covalent chemistry. Alkoxy groups influence formation rates and stability, revealing key factors for imine assembly control.

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Area of Science:

Organic Chemistry
Supramolecular Chemistry
Materials Science

Background:

Imine organic cages are typically formed via dynamic covalent chemistry, relying on error correction for assembly.
Understanding the factors influencing the formation kinetics and stability of these cages is crucial for their rational design.

Purpose of the Study:

To demonstrate the formation of kinetically trapped rylene diimide [2 + 3] cages.
To investigate the impact of substituents, specifically alkoxy groups, on cage formation kinetics and stability.
To explore the role of reaction intermediates and environmental factors in imine cage assembly.

Main Methods:

Synthesis of rylene diimide [2 + 3] cages using dynamic covalent chemistry.
Spectroscopic and analytical techniques to study formation kinetics and stability.
Investigating the effect of varying substituents (alkoxy groups) on precursor aldehydes.

Main Results:

High yields of kinetically trapped rylene diimide [2 + 3] cages were achieved.
Alkoxy groups on the aldehyde precursor exhibit dual effects: accelerating imine formation but reducing kinetic stability.
Aldehydes in solution and water concentration were identified as critical factors affecting cage stability.
[2 + 2] macrocycles were observed as intermediates in cage formation and decomposition.

Conclusions:

The study highlights the complex interplay of steric and electronic factors in kinetically controlled imine cage formation.
Alkoxy groups act as 'stereoelectronic chameleons,' influencing both reaction rate and product stability.
Understanding these factors is essential for controlling the thermodynamic versus kinetic regimes in imine assembly.