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All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for...
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Superior Metal-Organic Framework Activation with Dimethyl Ether.

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  • 1Department of Chemistry, Institution University of Michigan, 930 North University Avenue, Ann Arbor, MI 48109-1055, USA.

Angewandte Chemie (International Ed. in English)
|November 2, 2022
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Dimethyl ether (DME) offers a mild method for activating metal-organic frameworks (MOFs), achieving high surface areas without structural damage. This technique works for various MOFs, surpassing traditional thermal activation.

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Coordination ChemistryMetal-Organic FrameworksMicroporous MaterialsStructural CollapseSurface Area

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Area of Science:

  • Materials Science
  • Chemistry
  • Nanotechnology

Background:

  • Metal-organic frameworks (MOFs) are porous crystalline materials with diverse applications.
  • Traditional activation methods, like thermal treatment, can cause structural damage and limit accessible surface areas.
  • Developing mild and effective MOF activation strategies is crucial for their practical use.

Purpose of the Study:

  • To introduce and validate a novel activation method for MOFs using dimethyl ether (DME).
  • To demonstrate that DME activation preserves MOF structural integrity and enhances surface area.
  • To show the applicability of DME activation across different types of MOFs, including those with coordinatively unsaturated sites (CUS).

Main Methods:

  • Treatment of MOFs with dimethyl ether (DME), a low surface tension, low boiling point solvent.
  • Utilizing DME's ability to displace both pore-filling and coordinated solvent molecules.
  • Low-temperature evacuation of DME due to its high volatility.

Main Results:

  • Achieved high surface areas in MOFs, matching or exceeding those from existing protocols.
  • Preserved the structural integrity of MOFs during the activation process.
  • Successfully activated MOFs with and without coordinatively unsaturated sites (CUS).

Conclusions:

  • Dimethyl ether (DME) provides a superior, low-temperature activation method for MOFs.
  • This method enhances accessible surface area while maintaining framework stability.
  • DME activation is a versatile technique applicable to a broad range of MOF materials.