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This study synthesizes novel Al-oxo ring cocrystals using deep eutectic solvents (DESs). These ionic environments facilitate the encapsulation of halogen anions within the Al rings, forming unique ion pair cocrystal structures.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Traditional synthesis of Al-oxo rings often uses neutral solvent systems.
  • Deep eutectic solvents (DESs) offer a tunable ionic environment for chemical synthesis.
  • Quaternary ammonium salts with specific halide anions can template molecular ring formation.

Purpose of the Study:

  • To explore the synthesis of Al-oxo rings in ionic environments using DESs.
  • To investigate the formation of Al-oxo ring cocrystals with encapsulated halogen anions.
  • To characterize the structure and optical properties of the synthesized cocrystals.

Main Methods:

  • Synthesis of Al-oxo rings and cocrystals using DESs formed from quaternary ammonium salts (HBA) and phenols (HBD).
  • Utilized 'DES thermal' method for cocrystal synthesis.
  • Characterization through structural studies (X-ray crystallography) and theoretical calculations.

Main Results:

  • Five Al8 ion pair cocrystals were successfully synthesized with the general formula Q+ ⊂ {Cl@[Al8(BD)8(μ2-OH)4L12]}.
  • Structural analysis revealed phenol-coordinated Al rings and quaternary ammonium ion pairs forming the cocrystal structure.
  • Halogen anions were confined within the Al ring's central cavity, with quaternary ammonium cations in the organic shell.
  • Adaptive cocrystal binding was observed, especially with low-symmetry ligands like naphthoic and pyrene acids.

Conclusions:

  • DESs provide an effective ionic medium for synthesizing Al-oxo ring cocrystals.
  • The synthesized cocrystals exhibit a unique structure with encapsulated halogen anions and templated quaternary ammonium cations.
  • The study provides insights into the structure-property relationships, particularly optical behavior, of these novel cocrystal compounds.