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A Modular Approach to Inorganic Phosphazane Macrocycles.

Alex J Plajer1, Raúl García-Rodríguez1, Callum G M Benson1

  • 1Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.

Angewandte Chemie (International Ed. in English)
|April 22, 2017
PubMed
Summary

Researchers developed a modular method for synthesizing inorganic macrocycles using cyclophosphazane frameworks. This approach yields diverse trimeric and hexameric sulfur- and selenium-bridged structures, including the first air-stable and chiral variants.

Keywords:
X-ray structural analysismacrocyclesmodular synthesisphosphazanes

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Area of Science:

  • Inorganic Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Inorganic macrocycles with non-carbon backbones offer synthetic challenges and opportunities in host-guest and supramolecular chemistry.
  • Systematic assembly of inorganic molecules is crucial for developing novel materials and chemical systems.
  • Existing methods for inorganic macrocycle synthesis often lack modularity and high yields.

Purpose of the Study:

  • To develop a high-yielding, modular synthetic approach for inorganic macrocycles.
  • To explore the synthesis of trimeric and hexameric sulfur- and selenium-bridged macrocycles based on cyclophosphazane frameworks.
  • To investigate the competitive bridging abilities of sulfur and selenium and synthesize novel air-stable and chiral inorganic macrocycles.

Main Methods:

  • Utilized building blocks [S=(H)P(μ-NR)]2 for macrocycle synthesis.
  • Employed in situ generation of a key dianion intermediate [E....._ (S....._ )P(μ-NR)]22- (E=S, Se).
  • Reacted the dianion with electrophilic [ClP(μ-NR)]2 for hexameric rings or I2 for trimeric variants.

Main Results:

  • Demonstrated a versatile modular approach yielding a broad range of trimeric and hexameric S- and Se-bridged inorganic macrocycles.
  • Successfully synthesized the first air-stable and chiral inorganic macrocycles.
  • Highlighted the competitive bridging behavior between sulfur and selenium in these systems.

Conclusions:

  • The developed modular strategy provides efficient access to diverse inorganic macrocycles.
  • The synthesis of air-stable and chiral inorganic macrocycles opens new possibilities in host-guest and supramolecular chemistry.
  • This work advances the systematic assembly of inorganic molecules with non-carbon backbones.