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Updated: Feb 18, 2026

Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Covalent post-assembly modification in metallosupramolecular chemistry
Derrick A Roberts1, Ben S Pilgrim, Jonathan R Nitschke
1Department of Chemistry, University of Cambridge, Lensfield Road CB21EW, UK. jrn34@cam.ac.uk.
Covalent post-assembly modification (PAM) enhances metallosupramolecular complexes by enabling modular, late-stage functionalization. This review explores diverse PAM strategies, expanding synthetic possibilities in supramolecular chemistry.
Area of Science:
- Supramolecular Chemistry
- Organic Chemistry
- Materials Science
Background:
- Metallosupramolecular complexes are assembled structures held by metal-ligand coordination.
- Post-assembly modification (PAM) allows for late-stage functionalization of these complexes.
- Covalent PAM utilizes chemical reactions to modify pre-assembled structures.
Purpose of the Study:
- To review the diverse applications of covalent post-assembly modification (PAM) in metallosupramolecular chemistry.
- To highlight recent advancements in covalent PAM strategies.
- To provide insights into future challenges and opportunities in the field.
Main Methods:
- Review of existing literature on covalent PAM in metallosupramolecular chemistry.
- Categorization of covalent PAM strategies based on their application.
- Analysis of key examples and their significance.
Main Results:
- Covalent PAM enables modular derivatization of pre-assembled metallosupramolecular complexes.
- PAM strategies include metal-preorganized covalent synthesis, grafting functionalities, stabilizing metastable complexes, and triggering structural transformations.
- These methods significantly expand the accessible chemical space for supramolecular synthesis.
Conclusions:
- Covalent PAM is a versatile tool for tailoring metallosupramolecular architectures.
- Continued development of covalent PAM will drive innovation in supramolecular chemistry and materials science.
- Future research should focus on novel reaction development and exploring new applications.
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