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Reticular Chemistry and Isoreticular Expansion

2002
  • Omar M. Yaghi
  • Michael O’Keeffe
Synthesis of Metal-Organic Frameworks in a modern laboratory setting, focusing on reticular chemistry.

(generated image for illustration only)

Reticular chemistry is the design principle for MOFs, involving the assembly of predetermined molecular building blocks (metal nodes and organic linkers) into extended, ordered structures with predictable topologies. A key demonstration of this principle is the synthesis of isoreticular MOFs, where the underlying network topology is maintained while the pore size is systematically expanded by using progressively longer organic linkers.

Reticular chemistry elevates the synthesis of materials from a trial-and-error process to a more deterministic, design-based science. It treats the metal clusters (Secondary Building Units, SBUs) and organic linkers as pre-defined geometric shapes (e.g., an octahedral SBU and a linear linker). By understanding the coordination preferences of the metal and the geometry of the linker, chemists can predict the resulting network topology before synthesis. The most famous example of this is the Isoreticular MOF (IRMOF) series, which is based on the archetypal MOF-5 structure. MOF-5 has a primitive cubic (pcu) topology formed from Zn4O octahedral SBUs and linear 1,4-benzenedicarboxylate (BDC) linkers.

The concept of isoreticular expansion was demonstrated by replacing the BDC linker with longer, but geometrically similar, dicarboxylate linkers like 2,6-naphthalenedicarboxylate (NDC) or 4,4′-biphenyldicarboxylate (BPDC). The resulting materials, IRMOF-8 and IRMOF-10 respectively, retained the same pcu network topology as MOF-5 but featured significantly larger pores. This systematic variation allowed for a direct correlation between linker length, pore size, and properties like gas uptake capacity, proving that MOF properties could be fine-tuned in a highly controlled manner. This principle has been extended to numerous other network topologies and building block combinations, solidifying MOFs as a prime example of programmable matter at the molecular level.

UNESCO Nomenclature: 2203
– Inorganic chemistry

Type

Design Principle

Disruption

Foundational

Usage

Widespread Use

Precursors

  • concepts of supramolecular chemistry by jean-marie lehn
  • crystal engineering principles developed by gerhard schmidt
  • development of single-crystal x-ray diffraction for structure determination
  • synthesis of early coordination polymers
  • topological analysis of crystal structures

Applications

  • systematic tuning of pore size for selective molecular sieving
  • rational design of catalysts with controlled active site spacing
  • fundamental studies of gas adsorption in confined spaces
  • creation of hierarchical porous structures
  • design of frameworks for encapsulating large molecules like proteins

Patents:

NA

Potential Innovations Ideas

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Related to: reticular chemistry, isoreticular, MOF, irMOF, crystal engineering, topology, secondary building unit, SBU, rational design, pore size tuning.

Historical Context

Reticular Chemistry and Isoreticular Expansion

1990
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1997
2002
2015-09-14
1986
1991
1995
2000
2004

(if date is unknown or not relevant, e.g. "fluid mechanics", a rounded estimation of its notable emergence is provided)

Related Invention, Innovation & Technical Principles

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