4.6 Article

Single Crystal to Single Crystal (SC-to-SC) Transformation from a Nonporous to Porous Metal-Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 15, Pages 5962-5971

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201405684

Keywords

cross-coupling; heterogeneous catalysis; metal-organic frameworks; strontium; structure elucidation

Funding

  1. FCT [SFRH/BPD/71798/2010]
  2. FEDER through Programa Operacional Factores de Competitividade-COMPETE
  3. national funds through FCT-Fundacao para a Ciencia e Tecnologia within CICECO project [FCOMP-01-0124-FERDER-037271, Pest-C/CTM/LA0011/2013]

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A new amino-functionalized strontium-carboxylate-based metal-organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC-to-SC) transformation upon desolvation. Both structures have been characterized by single-crystal X-ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent -NH2 groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine-2-carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross-coupling reaction. The compound shows high activity towards the C-C cross-coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m(2) g(-1). The material also possesses good CO2 (8 wt%) and H-2 (1.87 wt%) adsorption capabilities.

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