# Post-synthetic modification of a MOF

> Functional groups can be added to a framework after it has formed. The amino groups that line the pores of IRMOF-3 react with acetic anhydride like an aniline would, turning into amides throughout the crystal while the framework stays intact. The powder pattern confirms the structure is kept, and ¹H NMR of digested crystals gives the conversion.

- Page: https://www.labcanvas.com/templates/metal-organic-frameworks/mof-post-synthetic-modification-irmof-3
- Open in the LabCanvas editor (LabCanvas account): https://www.labcanvas.com/editor.html?template=mof-postsynthetic-modification
- Updated: 2026-10-14
- Category: Metal–organic frameworks
- Method: Post-synthetic modification, bottom-up
- Starting materials: IRMOF-3, Zn₄O(NH₂-BDC)₃, made from zinc nitrate and 2-aminoterephthalic acid
- Product: The same cubic framework with acetamide groups (–NHCOCH₃) on the linkers
- Key result: Covalent modification inside the crystal without loss of the framework (Wang & Cohen 2007)
- Figure: 1920 × 1080 px, 82 editable layers (9 generated objects with settings)

## Steps

1. **Framework**: IRMOF-3: the MOF-5 net with an amino group on every linker (Eddaoudi et al. 2002)
2. **Acylate**: Crystals in a solution of acetic anhydride: –NH₂ → –NHCOCH₃, acetic acid released (Wang & Cohen 2007)
3. **Check the framework**: Powder pattern unchanged: the crystal survives the reaction
4. **Measure conversion**: Crystals digested in acid; ¹H NMR of the linkers gives the ratio of amide to amine

## Strengths

- Groups that would not survive MOF synthesis can be added afterwards
- One parent framework gives many products

## Limitations

- Reagents must fit through the pores
- Conversion can be incomplete deep in large crystals

## Uses

- Tuning pore chemistry for adsorption and separation
- Anchoring catalysts and metal sites

## References

1. Wang & Cohen, “Postsynthetic Covalent Modification of a Neutral Metal−Organic Framework”, J. Am. Chem. Soc. 2007. https://doi.org/10.1021/ja074366o (primary)
2. Cohen, “Postsynthetic Methods for the Functionalization of Metal–Organic Frameworks”, Chem. Rev. 2012. https://doi.org/10.1021/cr200179u (review)
3. Eddaoudi et al., “Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage”, Science 2002. https://doi.org/10.1126/science.1067208 (method origin)

Credit: Redrawn and simplified after Wang & Cohen, JACS 2007 (doi:10.1021/ja074366o), Cohen, Chem. Rev. 2012 (doi:10.1021/cr200179u) and Eddaoudi et al., Science 2002 (doi:10.1126/science.1067208). Powder patterns schematic.

## Questions

**What does the “Post-synthetic modification of a MOF” template show?** Functional groups can be added to a framework after it has formed. The amino groups that line the pores of IRMOF-3 react with acetic anhydride like an aniline would, turning into amides throughout the crystal while the framework stays intact. The powder pattern confirms the structure is kept, and ¹H NMR of digested crystals gives the conversion.

**What are the steps shown in “Post-synthetic modification of a MOF”?** 1. Framework: IRMOF-3: the MOF-5 net with an amino group on every linker (Eddaoudi et al. 2002). 2. Acylate: Crystals in a solution of acetic anhydride: –NH₂ → –NHCOCH₃, acetic acid released (Wang & Cohen 2007). 3. Check the framework: Powder pattern unchanged: the crystal survives the reaction. 4. Measure conversion: Crystals digested in acid; ¹H NMR of the linkers gives the ratio of amide to amine.

**What are the starting materials and the product?** Starting materials: IRMOF-3, Zn₄O(NH₂-BDC)₃, made from zinc nitrate and 2-aminoterephthalic acid. Product: The same cubic framework with acetamide groups (–NHCOCH₃) on the linkers.

**Which papers is “Post-synthetic modification of a MOF” based on?** Wang & Cohen, “Postsynthetic Covalent Modification of a Neutral Metal−Organic Framework”, J. Am. Chem. Soc. 2007 (doi:10.1021/ja074366o); Cohen, “Postsynthetic Methods for the Functionalization of Metal–Organic Frameworks”, Chem. Rev. 2012 (doi:10.1021/cr200179u); Eddaoudi et al., “Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage”, Science 2002 (doi:10.1126/science.1067208).

**Can I edit the “Post-synthetic modification of a MOF” template?** Yes. Open it in the LabCanvas editor: all 82 layers are editable, including 9 generated objects (structures, plots, equipment) with their own settings. Change the text, colours and layout, then export PNG, TIFF, SVG or PDF.

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