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Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework
Yong-Sheng Wei1, Mei Zhang1, Pei-Qin Liao1
1MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry &Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Nature Communications
|September 19, 2015
Summary
Porous coordination frameworks with open metal sites act as precise templates for chemical synthesis. This study demonstrates their use in templating [2+2+2] cyclotrimerization reactions, creating rigid, porous materials.
Area of Science:
- Materials Science
- Supramolecular Chemistry
- Chemical Synthesis
Background:
- Supramolecular confinement in nanopores is a key strategy for controlling chemical reactions.
- Open metal sites in porous materials offer potential as precise synthetic templates.
Purpose of the Study:
- To investigate the use of open metal sites in porous coordination frameworks as templates for precision synthesis.
- To demonstrate the [2+2+2] cyclotrimerization of specific monomers using a Fe(III) dicarboxylate framework.
Main Methods:
- Utilized a Fe(III) dicarboxylate framework with triangularly arranged metal sites.
- Employed in situ single-crystal X-ray diffraction to observe the reaction mechanism.
- Synthesized organonitrile, alkyne, and alkene monomers with pyridyl groups.
Main Results:
- The Fe(III) open metal sites successfully templated the [2+2+2] cyclotrimerization reaction.
- Monomers coordinated to Fe(III) centers, bringing unsaturated groups into proximity for cyclization.
- The resulting trimers formed tripodal ligands, stabilizing Fe(III) ions and creating a rigid, porous material with zero thermal expansion and a large surface area.
Conclusions:
- Open metal sites in porous coordination frameworks provide powerful and strict templates for precision chemical synthesis.
- This approach leads to the formation of highly stable, porous materials with unique properties like guest-proof zero thermal expansion.
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