A 2020 study reported P12L24, a porphyrin-based molecular cage about 5.3 nanometers across. Its authors called it, to their knowledge, the largest pure organic synthetic cage reported at the time. The structure is notable for its scale and construction, but the record claim needs qualification: a 2024 review still described it as the largest porphyrin organic cage, while the available evidence does not establish a comprehensive ranking of every organic cage in 2026.
What the researchers built
Koo and colleagues assembled P12L24 from 12 square-shaped porphyrin units and 24 bent organic linkers. The name reflects those component counts, making 36 components in total. The cage was made in a one-pot, template-free process, meaning the reported assembly did not rely on a separate template to shape the structure.
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Single-crystal X-ray analysis showed a cuboctahedral architecture: a polyhedral form with square and triangular faces. The measured overall diameter was approximately 5.3 nm, according to the 2020 paper in Chem (Koo et al., “Gigantic Porphyrinic Cages”).
How large is its internal space?
The external diameter and the hollow interior are different measurements. A 2022 review gives the internal cavity diameter as 4.3 nm, compared with the approximately 5.3 nm overall diameter reported from the crystal structure. The cavity figure is attributed to that review, not presented as the same measurement as the cage’s outer span (Chemical Reviews, 2022).
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Why the “largest” claim is qualified
The authors’ exact wording was: “To the best of our knowledge, it represents the largest, pure organic synthetic cage reported so far.” That phrasing limits the claim to what they knew when publishing in 2020; it is not an assertion that every cage worldwide was independently ranked.
A 2024 review continued to call P12L24 the largest porphyrin organic cage. That supports its distinction within the porphyrin-cage category through that review, but does not establish that it remains the largest of every class of pure organic synthetic cage in 2026 (Chemical Science, 2024).
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Comparisons between molecular cages also depend on what is being compared: overall diameter or cavity size, purely organic composition or metal-containing structure, and measurements from a crystal structure or another method. Keeping those distinctions intact is essential to interpreting a superlative.
What the cage demonstrated in the lab
Photooxidation
The 2020 study reported that cage 3a catalyzed photooxidation of dihydroxynaphthalene derivatives in a heterogeneous setting. A 2024 review summarized a size effect in which larger substrates achieved higher conversion than smaller porphyrin cages. These are laboratory findings, not evidence of a commercial photocatalyst or deployed process.
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Insertion of a long linker
The researchers also inserted an approximately 4 nm linear pillar linker into a zinc-metallated version of the cage, Zn-P12L24, in solution. This demonstration points to a way of modifying the cage interior and exploring more complex architectures; it does not mean the cage is a practical storage or delivery product.
Why making a cage this large was difficult
A 2022 review describes several obstacles in the synthesis: solubility challenges, polymeric byproducts, and formation of smaller cages that were entropically favored. In other words, assembling the desired large structure competed with pathways that were easier for the system to form. The one-pot, template-free result is significant in that context, although the reported difficulties underline that this is specialized molecular synthesis rather than a routine manufacturing method.
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What the result means
P12L24 is a striking example of how large a covalent porphyrin cage could be assembled and structurally characterized. Its 12 porphyrins, 24 linkers, cuboctahedral form, and separable external and internal dimensions make the result concrete. Its strongest defensible superlative remains the authors’ qualified 2020 claim, with later review support specifically for its standing among porphyrin cages.
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