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Covalent Metal–Organic Frameworks: Fusion of Covalent Organic Frameworks and Metal–Organic Frameworks

Authors: Rong-Jia Wei,Xiao Luo,Guo-Hong Ning,Dan Li
Publisher: American Chemical Society (ACS)
Publish date: 2025-2-21
ISSN: 0001-4842 DOI: 10.1021/acs.accounts.4c00774
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In your strategy for constructing CMOFs via preassembled metal complexes/clusters with reactive sites (e.g., –CHO, –NH₂) linked through dynamic covalent chemistry (DCC), you emphasize enhanced structural predictability and chemical stability. However, considering that imine-based linkages are known to exhibit limited hydrolytic stability, particularly under humid or acidic conditions, how do you reconcile this with your claim of “high chemical stability even under harsh conditions”?

Moreover, has any quantitative assessment (e.g., long-term water stability tests, pH-cycling durability, or catalytic performance retention in aqueous media) been conducted to support this stability claim, especially in comparison to conventional MOFs or COFs? If not, do you consider the imine-based DCC approach fundamentally limiting the application of CMOFs in environments requiring moisture or pH robustness?

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1 week, 6 days ago

That’s actually a fair point about the typical hydrolytic sensitivity of imine bonds. But to be honest, the authors here aren’t claiming that all imine-based frameworks are universally stable; rather, they emphasize how preassembled metal clusters and their strategic design help improve overall structural integrity. The DCC approach, when paired with robust metal–ligand assemblies like Cu-CTUs or even imide/boroxine-based linkages (which are also mentioned), seems to offer a balance of reactivity and stability.

Also, while the paper doesn’t godeep into long-term pH cycling or water-soak tests (which would be great follow-ups), there are several performance tests in aqueous or catalytic media (like in gold recovery, CO2 conversion, etc.) that indirectly show durability. So, maybe  “high chemical stability under harsh conditions” could’ve been phrased more specifically , but there’s definitely substance behind that claim in the context of their framework design.

Anyway, just my take; happy for the authors to confirm or correct me!

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