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PreprintCC BYChemRxiv

A Scalable One-Pot Strategy for Porphyrin Metal–Organic Frameworks via In situ Linker Synthesis

  • Anna Sinelshchikova1,2,3,4
  • Roberto Fernández de Luis1,2
  • Ibai Bilbao Zulaika5,6
  • Sofia Castro7,8
  • Pedro Martins9,10
  • Stefan Wuttke11
  • Alessia Giordana12
  • Emanuele Priola12
  • Senentxu Lanceros-Méndez1,2,3,4,7,8
  • Eliano Diana12
  • Bettina Baumgartner13,14
  • Jacopo Andreo1,2
14 affiliations
  1. 1BCMaterials
  2. 2Basque Center for Materials, Applications and Nanostructures, UPV/EHU Science Park
  3. 3IKERBASQUE
  4. 4Basque Foundation for Science
  5. 5Department of Organic and Inorganic Chemistry, Faculty of Science and Technology
  6. 6University of the Basque Country (UPV/EHU
  7. 7Physics Centre of Minho and Porto Universities (CF-UM-UP) and LaPMET - Laboratory of Physics for Materials and Emergent Technologies
  8. 8Universidade do Minho
  9. 9Centre of Molecular and Environmental Biology
  10. 10University of Minho
  11. 11Academic Centre for Materials and Nanotechnology, AGH University of Krakow, al. Adama Mickiewicza 30, Kraków, Poland, 30-059
  12. 12Department of Chemistry, University of Turin, Via Pietro Giuria 7, Torino, Italy, 10125
  13. 13Van’t Hoff Institute for Molecular Sciences
  14. 14University of Amsterdam
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Abstract

Porphyrin metal–organic frameworks (pMOFs) are highly versatile materials for catalysis, energy, and environmental applications, yet their widespread use is limited by the cost and multistep synthesis of porphyrin linkers. Here, we report a one-pot synthetic strategy that integrates porphyrin formation and MOF crystallization, enabling the direct assembly of zirconium-based pMOFs from simple molecular precursors. This approach eliminates the need for linker isolation and purification, significantly reducing synthetic complexity and resource consumption. The method is demonstrated for the benchmark framework PCN-224 and its zinc metalloporphyrin analogue, yielding crystalline, porous materials at multigram scale. Notably, the resulting materials exhibit enhanced mesoporosity, which improves mass transport and enables superior adsorption of large organic dyes, despite lower BET surface areas compared to conventionally synthesized analogues. Importantly, we further demonstrate the generality of this approach by synthesizing USTC-9(Fe), a framework with distinct metal nodes and porphyrin linker geometry. This work establishes a versatile platform for coupling complex linker synthesis with framework assembly, offering a sustainable and scalable route to functional pMOFs and broadening the scope of in situ linker formation in reticular chemistry.

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Cite

BibTeXRIS
BibTeX
@misc{sinelshchikova2026scalable,
  title = {{A Scalable One-Pot Strategy for Porphyrin Metal–Organic Frameworks via In situ Linker Synthesis}},
  author = {Anna Sinelshchikova and Roberto Fernández de Luis and Ibai Bilbao Zulaika and Sofia Castro and Pedro Martins and Stefan Wuttke and Alessia Giordana and Emanuele Priola and Senentxu Lanceros-Méndez and Eliano Diana and Bettina Baumgartner and Jacopo Andreo},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15002452/v2},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15002452/v2},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - A Scalable One-Pot Strategy for Porphyrin Metal–Organic Frameworks via In situ Linker Synthesis
AU  - Anna Sinelshchikova
AU  - Roberto Fernández de Luis
AU  - Ibai Bilbao Zulaika
AU  - Sofia Castro
AU  - Pedro Martins
AU  - Stefan Wuttke
AU  - Alessia Giordana
AU  - Emanuele Priola
AU  - Senentxu Lanceros-Méndez
AU  - Eliano Diana
AU  - Bettina Baumgartner
AU  - Jacopo Andreo
PY  - 2026
DA  - 2026/10/11
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15002452/v2
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15002452/v2
AB  - Porphyrin metal–organic frameworks (pMOFs) are highly versatile materials for catalysis, energy, and environmental applications, yet their widespread use is limited by the cost and multistep synthesis of porphyrin linkers. Here, we report a one-pot synthetic strategy that integrates porphyrin formation and MOF crystallization, enabling the direct assembly of zirconium-based pMOFs from simple molecular precursors. This approach eliminates the need for linker isolation and purification, significantly reducing synthetic complexity and resource consumption. The method is demonstrated for the benchmark framework PCN-224 and its zinc metalloporphyrin analogue, yielding crystalline, porous materials at multigram scale. Notably, the resulting materials exhibit enhanced mesoporosity, which improves mass transport and enables superior adsorption of large organic dyes, despite lower BET surface areas compared to conventionally synthesized analogues. Importantly, we further demonstrate the generality of this approach by synthesizing USTC-9(Fe), a framework with distinct metal nodes and porphyrin linker geometry. This work establishes a versatile platform for coupling complex linker synthesis with framework assembly, offering a sustainable and scalable route to functional pMOFs and broadening the scope of in situ linker formation in reticular chemistry.
ER  -