N-centered hexazirconium chloride clusters: excision and redox chemistry

Area of Science:

• Inorganic Chemistry
• Materials Science
• Electrochemistry

Background:

• Zirconium halide clusters are known for their unique structures and reactivity.
• The incorporation of interstitial atoms, such as nitrogen, can significantly alter cluster properties.
• Understanding the electronic structure and redox behavior of these clusters is crucial for potential applications.

Purpose of the Study:

• To synthesize and characterize novel N-centered zirconium cluster complexes.
• To investigate the electrochemical properties of a series of related cluster ions.
• To establish structure-property relationships within these zirconium cluster systems.

Main Methods:

• Synthesis of zirconium-nitrogen clusters using bis(triphenylphosphine)iminium chloride (PPNCl).
• Characterization using Nitrogen-15 Nuclear Magnetic Resonance ((15)N NMR) spectroscopy.
• Electrochemical studies employing cyclic voltammetry (CV) in acetonitrile.
• Isolation and structural characterization of new cluster complexes via X-ray diffraction.

Main Results:

• The solid-state Zr(6)Cl(15)N was converted to the soluble cluster ion [(Zr(6)NCl(12))Cl(6)](3-).
• Cyclic voltammetry revealed multiple reversible redox waves for [(Zr(6)ZCl(12))Cl(6)](n-) (Z = Be, B, C, N) cluster ions.
• A reversible redox couple was identified for the [(Zr(6)NCl(12))Cl(6)](3-/4-) system.
• Reduced cluster ions, including [(Zr(6)NCl(12))Cl(6)](4-), were successfully prepared and isolated.

Conclusions:

• Novel N-centered zirconium cluster complexes have been successfully synthesized and structurally elucidated.
• The electrochemical behavior of these clusters is systematically tunable and well-defined.
• These findings contribute to the understanding of redox-active cluster chemistry and open avenues for new materials design.