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Crystalline Assembly and Solvent‐induced Solid‐state Transformation of 1D Zigzag Chains Based on Sulfonylcalix[4]arene Trinuclear Co(II) and Zn(II) Clusters

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New 1D zigzag coordination polymers were generated using sulfonylcalix[4]arene, metal M2+ cations (M=Co or Zn) and rigid planar N-shaped linkers (stilbene-4,4′-dicarboxylic acid or azobenzene-4,4-dicarboxylic acid). The flexibility of crystal packing allowed to observe dynamic reversible solid -state transformation upon the release/uptake of solvent DMSO molecules for one of the CPs.


Abstract

The reproducible formation, in mild conditions, of three new 1D zigzag coordination polymers using sulfonylcalix[4]arene (TCASO2), metal M2+ cations (M=Co or Zn) and rigid planar N-shaped linkers (stilbene-4,4′-dicarboxylic acid (1-2H) or azobenzene-4,4′-dicarboxylic acid (2-2H)) is reported. The obtained coordination compounds (1-TCASO2Zn3 , 1-TCASO2Co3 and 2-TCASO2Zn3 ) are characterized in the crystalline phase using single crystal and powder X-ray diffraction (XRD and XRPD), TGA and IR-spectroscopy. The three compounds present the same coordination pattern and 1-TCASO2Zn3 and 2-TCASO2Zn3 reveal to be isostructural. Due to a high porosity and amount of accommodated solvent molecules hosted in the network, the generated rigid 1D chains are capable to undergo a reversible dynamic solid-state transformation in terms of crystal packing, accompanied with release/uptake of DMSO molecules leading to compression/stretching of the unit cell along one of the crystallographic axis which was attested by Rietveld refinement on XRPD data.

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