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Octahedral {Ta6I12} Clusters.

Maxim V Shamshurin1, Maxim A Mikhaylov1, Taisia Sukhikh1

  • 1Nikolaev Institute of Inorganic Chemistry SB RAS , 3 Akad. Lavrentiev Ave. , Novosibirsk 630090 , Russian Federation.

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|June 29, 2019
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Summary
This summary is machine-generated.

Tantalum powder reacts with iodine to form Ta6I14 clusters, which can be aquated to form intensely colored [Ta6I12(H2O)6]2+. This aqua complex exhibits enhanced stability when associated with polystyrenesulfonate (PSS).

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Solid-State Chemistry

Background:

  • Tantalum-iodine compounds are known for their unique cluster structures.
  • The {M6(μ-X)12} cluster family offers intriguing electronic and structural properties.
  • Understanding the reactivity and stability of these clusters is crucial for potential applications.

Purpose of the Study:

  • To synthesize and characterize tantalum-iodine clusters, specifically Ta6I14.
  • To investigate the aquation of Ta6I14 and the properties of the resulting aqua complex.
  • To explore methods for enhancing the stability of the tantalum aqua cluster.

Main Methods:

  • High-temperature reaction of tantalum powder with iodine.
  • Aquation of the tantalum cluster in aqueous solutions.
  • Crystal structure determination using X-ray diffraction.
  • Cyclic voltammetry for electrochemical analysis.
  • Quantum chemical calculations for theoretical insights.
  • Complexation with polystyrenesulfonate (PSS) for stability enhancement.

Main Results:

  • Synthesis of Ta6I14 and its subsequent aquation to form the intensely colored [Ta6I12(H2O)6]2+.
  • Crystal structures of the aqua and DMF adducts were determined, revealing Ta-Ta bond lengths around 2.95 Å.
  • Electrochemical studies showed two quasi-reversible one-electron oxidations for the aqua complex.
  • Quantum chemical calculations confirmed the experimental geometry and the Ta-centered nature of the frontier orbitals.
  • Formation of nanoparticle associates with PSS significantly enhanced the long-term stability of the aqua complex solutions.

Conclusions:

  • The synthesis and characterization of novel tantalum-iodine clusters and their aqua complexes were successful.
  • The [Ta6I12(H2O)6]2+ complex exhibits interesting electrochemical properties and a stable structure.
  • Polystyrenesulfonate (PSS) provides an effective strategy for stabilizing these tantalum aqua clusters in aqueous media.