# Post-synthetic modification, stability, conductivity

> Changing and keeping MOFs on one page: the five kinds of post-synthetic modification (covalent, dative, linker exchange, metal-ion exchange, metalation by ALD), how water hydrolyses a metal–linker bond, hard–soft pairing of metal and linker, the strategies that make MOFs water-stable, the conductive honeycomb Ni₃(HITP)₂ and the routes charge takes through a MOF. Every statement and number is quoted from the cited papers.

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- Open in the LabCanvas editor (LabCanvas account): https://www.labcanvas.com/editor.html?template=mof-psm-stability-conductivity
- Updated: 2026-10-14
- Category: MOF guides
- Method: Modification, stability and conductivity
- Product: Post-synthetically modified, water-stable and electrically conductive MOFs
- Key result: Clusters, linkers and layers drawn by LabCanvas from the cited structures; reactions and charge paths are schematic, and no panel is a measurement
- Figure: 1920 × 1080 px, 45 editable layers (6 generated objects with settings)

## Steps

1. **Five kinds of PSM**: Covalent: the pendant amino groups of IRMOF-3 react with linear alkyl anhydrides to give amides, from ~99% to ~7% conversion as the chain grows, the products staying crystalline and microporous (Tanabe 2008); covalent PSM of a neutral MOF (Wang & Cohen 2007) and the post-synthetic methods are reviewed (Cohen 2012). Dative: the open Mg²⁺ of Mg₂(dobpdc) took N,N′-dimethylethylenediamine, and mmen–Mg₂(dobpdc) takes up 2.0 mmol/g CO₂ at 0.39 mbar and 25 °C (McDonald 2012); MOF-74 has been functionalised mostly this way (Lim 2021). Linker exchange (SALE) gives MOFs unobtainable by direct synthesis (Karagiaridi 2014), pillars exchanging crystal to crystal (Burnett 2011). Ion metathesis turns MOF-5’s Zn₄O clusters into MZn₃O with Ti³⁺, V²⁺, Cr²⁺, Cr³⁺, Mn²⁺ or Fe²⁺ (Brozek & Dincă 2013). ALD in MOFs (AIM) metalates from the gas phase, enabled by NU-1000 (Mondloch 2013); Ni ions installed on its Zr₆ nodes stayed isolated single sites (Li 2016)
2. **How water breaks a MOF**: MOFs degrade as metal–ligand bonds break: water molecules attack the weak coordination bonds and displace the ligands (Ding 2019); water stability and adsorption in MOFs have been reviewed (Burtch 2014). Steaming tests and cluster calculations showed that the strength of the bond between the metal oxide cluster and the bridging linker governs hydrothermal stability, more than framework flexibility (Low 2009). Moisture can collapse Zn₄O-based MOFs irreversibly; IRMOF-3 degrades at a lower humidity than MOF-5 (Guo 2015)
3. **Hard–soft pairing**: Thermodynamic stability rests on the metal–ligand bond strength, which HSAB theory can predict: high-valent hard acids (Zr⁴⁺, Cr³⁺, Al³⁺, Fe³⁺) bind O-donor carboxylates strongly, and low-valent soft acids (Zn²⁺, Co²⁺, Ni²⁺, Fe²⁺, Ag⁺) build stable MOFs with N-donor linkers; MIL-101(Cr) is stable in water at pH 0–12 for 2 months (Ding 2019). Stable MOFs fall into two families, high-valency metal–carboxylate and low-valency metal–azolate frameworks (Yuan 2018). UiO-66 decomposes only above 500 °C and stays crystalline after 10 tons/cm² (Cavka 2008); ZIF-8 is remarkably resistant to boiling alkaline water and organic solvents (Park 2006)
4. **Making MOFs water-stable**: UiO-66’s 12-connected nodes are considered responsible for its high thermal and chemical stability (Cliffe 2014). A MOF-5 with 2,5-dimethyl linkers kept its H₂ uptake after four days in ambient air, the water-repellent groups protecting the weak bonds; dense, rigid frameworks of highly connected building blocks tolerate partial lattice collapse, interpenetration locks the linkers in place, and a hydrophobic polydimethylsiloxane (PDMS) coating prevented the attack of water (Ding 2019)
5. **Ni₃(HITP)₂**: Ni₃(HITP)₂ forms from 2,3,6,7,10,11-hexaaminotriphenylene and Ni²⁺ in aqueous ammonia in air: a 2D MOF with conductivities of 2 S·cm⁻¹ (pellet) and 40 S·cm⁻¹ (film), records for MOFs (Sheberla 2014). Square-planar Ni joins the triphenylene linkers into honeycomb layers stacked near-eclipsed 3.35 Å apart, with micropores of ~1.6 nm; single crystals of Cu₃(HHTP)₂ conduct about as well across the layers (1.5 S/cm) as within them (0.5 S/cm) (Xie 2020). Most MOFs are electrical insulators, but a few combine porosity with excellent conductivity (Sun 2016)
6. **Charge routes**: Four strategies give conductive MOFs: through-bond chains of metals and ligand donor atoms, extended π–d conjugation over metals and whole ligands, through-space π–π stacking, and guests in the pores; swapping the O donors of Mn₂(DOBDC) for S raised the conductivity by about an order of magnitude, and where no band-like path exists, charge hops between redox-active metals or linkers (Xie 2020). TCNQ loaded into thin films of HKUST-1 bridges the copper paddlewheels: the conductivity is tunable over six orders of magnitude, up to 7 S/m (Talin 2014)

## Strengths

- Linker exchange gives MOFs unobtainable by direct synthesis (Karagiaridi 2014)
- MIL-101(Cr) is stable in water at pH 0–12 for 2 months (Ding 2019)
- TCNQ makes the conductivity of HKUST-1 films tunable over six orders of magnitude (Talin 2014)

## Limitations

- Covalent conversion of IRMOF-3 fell from ~99% to ~7% as the anhydride chain grew (Tanabe 2008)
- Moisture can collapse Zn₄O-based MOFs irreversibly (Guo 2015)
- Most MOFs are electrical insulators (Sun 2016)

## References

1. Tanabe, Wang & Cohen, “Systematic functionalization of a metal-organic framework via a postsynthetic modification approach”, J. Am. Chem. Soc. 2008. https://doi.org/10.1021/ja801848j (primary)
2. Wang & Cohen, “Postsynthetic covalent modification of a neutral metal-organic framework”, J. Am. Chem. Soc. 2007. https://doi.org/10.1021/ja074366o (primary)
3. McDonald et al., “Capture of carbon dioxide from air and flue gas in the alkylamine-appended metal-organic framework mmen-Mg₂(dobpdc)”, J. Am. Chem. Soc. 2012. https://doi.org/10.1021/ja300034j (primary)
4. Lim et al., “Amine-tagged fragmented ligand installation for covalent modification of MOF-74”, Angew. Chem. Int. Ed. 2021. https://doi.org/10.1002/anie.202100456 (primary)
5. Karagiaridi et al., “Solvent-assisted linker exchange: an alternative to the de novo synthesis of unattainable metal-organic frameworks”, Angew. Chem. Int. Ed. 2014. https://doi.org/10.1002/anie.201306923 (primary)
6. Burnett et al., “Stepwise synthesis of metal-organic frameworks: replacement of structural organic linkers”, J. Am. Chem. Soc. 2011. https://doi.org/10.1021/ja201911v (primary)
7. Brozek & Dincă, “Ti³⁺-, V²⁺/³⁺-, Cr²⁺/³⁺-, Mn²⁺-, and Fe²⁺-substituted MOF-5 and redox reactivity in Cr- and Fe-MOF-5”, J. Am. Chem. Soc. 2013. https://doi.org/10.1021/ja4064475 (primary)
8. Mondloch et al., “Vapor-phase metalation by atomic layer deposition in a metal-organic framework”, J. Am. Chem. Soc. 2013. https://doi.org/10.1021/ja4050828 (primary)
9. Li et al., “Sintering-resistant single-site nickel catalyst supported by metal-organic framework”, J. Am. Chem. Soc. 2016. https://doi.org/10.1021/jacs.5b12515 (primary)
10. Ding, Cai & Jiang, “Improving MOF stability: approaches and applications”, Chem. Sci. 2019. https://doi.org/10.1039/c9sc03916c (primary)
11. Low et al., “Virtual high throughput screening confirmed experimentally: porous coordination polymer hydration”, J. Am. Chem. Soc. 2009. https://doi.org/10.1021/ja9061344 (primary)
12. Guo et al., “Water sensitivity in Zn₄O-based MOFs is structure and history dependent”, J. Am. Chem. Soc. 2015. https://doi.org/10.1021/ja512382f (primary)
13. Yuan et al., “Stable metal-organic frameworks: design, synthesis, and applications”, Adv. Mater. 2018. https://doi.org/10.1002/adma.201704303 (primary)
14. Cavka et al., “A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability”, J. Am. Chem. Soc. 2008. https://doi.org/10.1021/ja8057953 (primary)
15. Park et al., “Exceptional chemical and thermal stability of zeolitic imidazolate frameworks”, Proc. Natl. Acad. Sci. USA 2006. https://doi.org/10.1073/pnas.0602439103 (primary)
16. Cliffe et al., “Correlated defect nanoregions in a metal-organic framework”, Nat. Commun. 2014. https://doi.org/10.1038/ncomms5176 (primary)
17. Sheberla et al., “High electrical conductivity in Ni₃(2,3,6,7,10,11-hexaiminotriphenylene)₂, a semiconducting metal-organic graphene analogue”, J. Am. Chem. Soc. 2014. https://doi.org/10.1021/ja502765n (primary)
18. Xie, Skorupskii & Dincă, “Electrically conductive metal-organic frameworks”, Chem. Rev. 2020. https://doi.org/10.1021/acs.chemrev.9b00766 (primary)
19. Sun, Campbell & Dincă, “Electrically conductive porous metal-organic frameworks”, Angew. Chem. Int. Ed. 2016. https://doi.org/10.1002/anie.201506219 (primary)
20. Talin et al., “Tunable electrical conductivity in metal-organic framework thin-film devices”, Science 2014. https://doi.org/10.1126/science.1246738 (primary)
21. Cohen, “Postsynthetic methods for the functionalization of metal-organic frameworks”, Chem. Rev. 2012. https://doi.org/10.1021/cr200179u (further reading)
22. Burtch, Jasuja & Walton, “Water stability and adsorption in metal-organic frameworks”, Chem. Rev. 2014. https://doi.org/10.1021/cr5002589 (further reading)

Credit: Drawn by LabCanvas after Cohen, Chem. Rev. 2012 (doi:10.1021/cr200179u), McDonald et al., J. Am. Chem. Soc. 2012, Brozek & Dincă, J. Am. Chem. Soc. 2013 and Mondloch et al., J. Am. Chem. Soc. 2013, and the papers in the details.

## Questions

**What does the “Post-synthetic modification, stability, conductivity” template show?** Changing and keeping MOFs on one page: the five kinds of post-synthetic modification (covalent, dative, linker exchange, metal-ion exchange, metalation by ALD), how water hydrolyses a metal–linker bond, hard–soft pairing of metal and linker, the strategies that make MOFs water-stable, the conductive honeycomb Ni₃(HITP)₂ and the routes charge takes through a MOF. Every statement and number is quoted from the cited papers.

**What are the steps shown in “Post-synthetic modification, stability, conductivity”?** 1. Five kinds of PSM: Covalent: the pendant amino groups of IRMOF-3 react with linear alkyl anhydrides to give amides, from ~99% to ~7% conversion as the chain grows, the products staying crystalline and microporous (Tanabe 2008); covalent PSM of a neutral MOF (Wang & Cohen 2007) and the post-synthetic methods are reviewed (Cohen 2012). Dative: the open Mg²⁺ of Mg₂(dobpdc) took N,N′-dimethylethylenediamine, and mmen–Mg₂(dobpdc) takes up 2.0 mmol/g CO₂ at 0.39 mbar and 25 °C (McDonald 2012); MOF-74 has been functionalised mostly this way (Lim 2021). Linker exchange (SALE) gives MOFs unobtainable by direct synthesis (Karagiaridi 2014), pillars exchanging crystal to crystal (Burnett 2011). Ion metathesis turns MOF-5’s Zn₄O clusters into MZn₃O with Ti³⁺, V²⁺, Cr²⁺, Cr³⁺, Mn²⁺ or Fe²⁺ (Brozek & Dincă 2013). ALD in MOFs (AIM) metalates from the gas phase, enabled by NU-1000 (Mondloch 2013); Ni ions installed on its Zr₆ nodes stayed isolated single sites (Li 2016). 2. How water breaks a MOF: MOFs degrade as metal–ligand bonds break: water molecules attack the weak coordination bonds and displace the ligands (Ding 2019); water stability and adsorption in MOFs have been reviewed (Burtch 2014). Steaming tests and cluster calculations showed that the strength of the bond between the metal oxide cluster and the bridging linker governs hydrothermal stability, more than framework flexibility (Low 2009). Moisture can collapse Zn₄O-based MOFs irreversibly; IRMOF-3 degrades at a lower humidity than MOF-5 (Guo 2015). 3. Hard–soft pairing: Thermodynamic stability rests on the metal–ligand bond strength, which HSAB theory can predict: high-valent hard acids (Zr⁴⁺, Cr³⁺, Al³⁺, Fe³⁺) bind O-donor carboxylates strongly, and low-valent soft acids (Zn²⁺, Co²⁺, Ni²⁺, Fe²⁺, Ag⁺) build stable MOFs with N-donor linkers; MIL-101(Cr) is stable in water at pH 0–12 for 2 months (Ding 2019). Stable MOFs fall into two families, high-valency metal–carboxylate and low-valency metal–azolate frameworks (Yuan 2018). UiO-66 decomposes only above 500 °C and stays crystalline after 10 tons/cm² (Cavka 2008); ZIF-8 is remarkably resistant to boiling alkaline water and organic solvents (Park 2006). 4. Making MOFs water-stable: UiO-66’s 12-connected nodes are considered responsible for its high thermal and chemical stability (Cliffe 2014). A MOF-5 with 2,5-dimethyl linkers kept its H₂ uptake after four days in ambient air, the water-repellent groups protecting the weak bonds; dense, rigid frameworks of highly connected building blocks tolerate partial lattice collapse, interpenetration locks the linkers in place, and a hydrophobic polydimethylsiloxane (PDMS) coating prevented the attack of water (Ding 2019). 5. Ni₃(HITP)₂: Ni₃(HITP)₂ forms from 2,3,6,7,10,11-hexaaminotriphenylene and Ni²⁺ in aqueous ammonia in air: a 2D MOF with conductivities of 2 S·cm⁻¹ (pellet) and 40 S·cm⁻¹ (film), records for MOFs (Sheberla 2014). Square-planar Ni joins the triphenylene linkers into honeycomb layers stacked near-eclipsed 3.35 Å apart, with micropores of ~1.6 nm; single crystals of Cu₃(HHTP)₂ conduct about as well across the layers (1.5 S/cm) as within them (0.5 S/cm) (Xie 2020). Most MOFs are electrical insulators, but a few combine porosity with excellent conductivity (Sun 2016). 6. Charge routes: Four strategies give conductive MOFs: through-bond chains of metals and ligand donor atoms, extended π–d conjugation over metals and whole ligands, through-space π–π stacking, and guests in the pores; swapping the O donors of Mn₂(DOBDC) for S raised the conductivity by about an order of magnitude, and where no band-like path exists, charge hops between redox-active metals or linkers (Xie 2020). TCNQ loaded into thin films of HKUST-1 bridges the copper paddlewheels: the conductivity is tunable over six orders of magnitude, up to 7 S/m (Talin 2014).

**Which papers is “Post-synthetic modification, stability, conductivity” based on?** Tanabe, Wang & Cohen, “Systematic functionalization of a metal-organic framework via a postsynthetic modification approach”, J. Am. Chem. Soc. 2008 (doi:10.1021/ja801848j); Wang & Cohen, “Postsynthetic covalent modification of a neutral metal-organic framework”, J. Am. Chem. Soc. 2007 (doi:10.1021/ja074366o); McDonald et al., “Capture of carbon dioxide from air and flue gas in the alkylamine-appended metal-organic framework mmen-Mg₂(dobpdc)”, J. Am. Chem. Soc. 2012 (doi:10.1021/ja300034j); Lim et al., “Amine-tagged fragmented ligand installation for covalent modification of MOF-74”, Angew. Chem. Int. Ed. 2021 (doi:10.1002/anie.202100456); Karagiaridi et al., “Solvent-assisted linker exchange: an alternative to the de novo synthesis of unattainable metal-organic frameworks”, Angew. Chem. Int. Ed. 2014 (doi:10.1002/anie.201306923); Burnett et al., “Stepwise synthesis of metal-organic frameworks: replacement of structural organic linkers”, J. Am. Chem. Soc. 2011 (doi:10.1021/ja201911v); Brozek & Dincă, “Ti³⁺-, V²⁺/³⁺-, Cr²⁺/³⁺-, Mn²⁺-, and Fe²⁺-substituted MOF-5 and redox reactivity in Cr- and Fe-MOF-5”, J. Am. Chem. Soc. 2013 (doi:10.1021/ja4064475); Mondloch et al., “Vapor-phase metalation by atomic layer deposition in a metal-organic framework”, J. Am. Chem. Soc. 2013 (doi:10.1021/ja4050828); Li et al., “Sintering-resistant single-site nickel catalyst supported by metal-organic framework”, J. Am. Chem. Soc. 2016 (doi:10.1021/jacs.5b12515); Ding, Cai & Jiang, “Improving MOF stability: approaches and applications”, Chem. Sci. 2019 (doi:10.1039/c9sc03916c); Low et al., “Virtual high throughput screening confirmed experimentally: porous coordination polymer hydration”, J. Am. Chem. Soc. 2009 (doi:10.1021/ja9061344); Guo et al., “Water sensitivity in Zn₄O-based MOFs is structure and history dependent”, J. Am. Chem. Soc. 2015 (doi:10.1021/ja512382f); Yuan et al., “Stable metal-organic frameworks: design, synthesis, and applications”, Adv. Mater. 2018 (doi:10.1002/adma.201704303); Cavka et al., “A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability”, J. Am. Chem. Soc. 2008 (doi:10.1021/ja8057953); Park et al., “Exceptional chemical and thermal stability of zeolitic imidazolate frameworks”, Proc. Natl. Acad. Sci. USA 2006 (doi:10.1073/pnas.0602439103); Cliffe et al., “Correlated defect nanoregions in a metal-organic framework”, Nat. Commun. 2014 (doi:10.1038/ncomms5176); Sheberla et al., “High electrical conductivity in Ni₃(2,3,6,7,10,11-hexaiminotriphenylene)₂, a semiconducting metal-organic graphene analogue”, J. Am. Chem. Soc. 2014 (doi:10.1021/ja502765n); Xie, Skorupskii & Dincă, “Electrically conductive metal-organic frameworks”, Chem. Rev. 2020 (doi:10.1021/acs.chemrev.9b00766); Sun, Campbell & Dincă, “Electrically conductive porous metal-organic frameworks”, Angew. Chem. Int. Ed. 2016 (doi:10.1002/anie.201506219); Talin et al., “Tunable electrical conductivity in metal-organic framework thin-film devices”, Science 2014 (doi:10.1126/science.1246738); Cohen, “Postsynthetic methods for the functionalization of metal-organic frameworks”, Chem. Rev. 2012 (doi:10.1021/cr200179u); Burtch, Jasuja & Walton, “Water stability and adsorption in metal-organic frameworks”, Chem. Rev. 2014 (doi:10.1021/cr5002589).

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