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Phase dependent structural perturbation of a robust multicomponent assembled icosahedral array.

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Bowl-shaped p-sulfonatocalix[4]arene molecules form compressed icosahedral arrays with yttrium ions. These structures maintain integrity in solution but rearrange geometrically.

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Area of Science:

  • Supramolecular Chemistry
  • Crystal Engineering
  • Materials Science

Background:

  • p-Sulfonatocalix[4]arene molecules are known for their ability to form self-assembled structures.
  • Metal-organic complexes involving lanthanide ions and organic ligands are of interest for their unique properties.

Purpose of the Study:

  • To investigate the solid-state assembly of p-sulfonatocalix[4]arene molecules with dipicolinate and yttrium(iii) ions.
  • To characterize the structural features, including axial compression, of the resulting icosahedral arrays.
  • To explore the behavior of these assemblies in solution.

Main Methods:

  • Single-crystal X-ray diffraction to determine the solid-state structure.
  • Hirshfeld surface analysis to quantify intermolecular interactions and assess compression.
  • Solution-based studies to observe structural changes upon dissolution.

Main Results:

  • Successfully assembled three-fold axially compressed icosahedral arrays of p-sulfonatocalix[4]arene.
  • Confirmed intricate binding of dipicolinate and yttrium(iii) ions within the icosahedral framework.
  • Observed that the icosahedral structures remain intact in solution but undergo geometrical rearrangement.

Conclusions:

  • The study demonstrates controlled self-assembly of complex supramolecular architectures with specific geometric constraints.
  • Axial compression in the solid state is a key feature, evidenced by Hirshfeld analysis.
  • The observed rearrangement in solution highlights the dynamic nature of these supramolecular systems.