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Postassembly Modification of Interior Spaces Within M12L24 Nanospheres
Eduard O Bobylev1, Bas de Bruin1, Joost N H Reek1
1van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, Amsterdam, 1098 XH, the Netherlands.
Angewandte Chemie (International Ed. in English)
|August 13, 2025
Summary
Post assembly modification (PAM) creates diverse M12L24 nanospheres with unique internal environments. This method efficiently generates and screens functional confined spaces using alkyl N-pyridinium carboxy aldehydes (ANCA).
Area of Science:
- Supramolecular Chemistry
- Materials Science
- Organic Synthesis
Background:
- Post assembly modification (PAM) has emerged as a key strategy in supramolecular chemistry over the last decade.
- PAM expands chemical diversity in supramolecular synthesis, enabling tailored functional materials.
- Existing methods for creating complex supramolecular structures can be limited in scope and efficiency.
Purpose of the Study:
- To apply post assembly modification (PAM) for the synthesis of M12L24 nanospheres with novel interior spaces.
- To introduce and utilize alkyl N-pyridinium carboxy aldehydes (ANCA) as an orthogonal functional group for PAM.
- To demonstrate the versatility of PAM in creating diverse confined environments within nanospheres.
Main Methods:
- Synthesis of M12L24 nanospheres as parent structures.
- Introduction of alkyl N-pyridinium carboxy aldehydes (ANCA) as a functional handle for modification.
- Quantitative post assembly modification (PAM) of nanospheres with various aniline derivatives.
Main Results:
- Successful creation of M12L24 nanospheres with unique and tunable interior spaces via PAM.
- Demonstration of quantitative PAM using ANCA with diverse aniline derivatives, yielding hydrophobic, chiral, and catalytic confined spaces.
- The parent nanospheres are easily characterized, facilitating efficient screening of secondary interactions and confined space properties.
Conclusions:
- PAM is a powerful and efficient methodology for generating multifunctional confined spaces within supramolecular nanostructures.
- The ANCA functional group provides an ideal platform for orthogonal PAM, enabling rapid diversification.
- This approach offers a fast and efficient tool for screening secondary interactions and exploring the properties of confined spaces.

