Article Review · Nature · 1999

MOF-5: The Framework That Started It All

PaperDesign and synthesis of an exceptionally stable and highly porous metal-organic framework
AuthorsH. Li, M. Eddaoudi, M. O'Keeffe, O. M. Yaghi
PublishedNature, 1999
DOI10.1038/46248
Read the Original Paper ↗

Before this paper, porous coordination polymers had a credibility problem: most collapsed the moment their guest solvent was removed. Li, Eddaoudi, O'Keeffe and Yaghi answered that objection with Zn4O(BDC)3, soon known simply as MOF-5, a cubic lattice of zinc-oxide clusters linked by terephthalate struts that stayed crystalline and porous after full evacuation.

The headline numbers were startling for 1999. A Langmuir surface area around 2,900 m2/g and a pore volume that dwarfed zeolites made MOF-5 the most porous crystalline material then known. Equally important was the conceptual claim: that the framework was designed, not discovered. The Zn4O cluster acts as a rigid octahedral joint, the linear dicarboxylate as a strut, and the resulting topology is predictable from those two choices. That single idea, geometry in, structure out, became reticular chemistry.

Reading it critically a quarter century later, two caveats deserve mention. First, MOF-5 is notoriously moisture sensitive; ambient humidity degrades the lattice within hours, a weakness the paper does not dwell on and which limited practical deployment for years. Second, the 'exceptionally stable' in the title refers to thermal stability of the evacuated framework, roughly 300 C, not chemical robustness, and casual readers have conflated the two ever since.

None of that diminishes the achievement. The paper compressed the design-synthesize-evacuate-measure loop into a template that thousands of groups then copied, and its gas sorption protocol became the field's standard proof of permanent porosity. If you read only one historical MOF paper, this is the one, but read it alongside a modern stability study so you know where the 1999 optimism needed later correction.

Reviewer's VerdictFoundational. Read it to understand why every MOF paper since cites it.

This review reflects the independent opinion of Team LR at MOFsResearch.com. It is an educational commentary on the cited publication and is not affiliated with or endorsed by the original authors or publisher. Verify all figures against the original paper before use.