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Homopolyatomic bismuth cluster compound Bi8[AlBr4]2: synthesis, structural characterization, and electronic structure
S M Gayomi K Samarakoon1, Chaila N Estrella1, Sviatoslav Baranets1
1Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, USA.
Acta Crystallographica. Section C, Structural Chemistry
|June 26, 2026
Summary
Researchers synthesized octabismuth(2+) bis(tetrabromidoaluminate), Bi8[AlBr4]2, using a Lewis acidic ionic liquid. This new bismuth cluster compound exhibits semiconducting properties with a 1.51 eV band gap.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Solid-State Chemistry
Background:
- Bismuth compounds are known for unique cluster structures and potential applications.
- Lewis acidic ionic liquids offer novel reaction media for synthesizing complex inorganic materials.
- Understanding the electronic properties of bismuth clusters is crucial for materials development.
Purpose of the Study:
- To synthesize and characterize a novel octabismuth cluster compound.
- To investigate the structural and electronic properties of Bi8[AlBr4]2.
- To explore the utility of Lewis acidic ionic liquids in cluster synthesis.
Main Methods:
- One-pot synthesis using BiBr3, AlBr3, and Bi in a Lewis acidic ionic liquid ([BMIm]Br·3.95AlBr3).
- Single-crystal X-ray diffraction for structural determination.
- Electronic structure calculations (molecular and periodic approaches).
Main Results:
- Successfully synthesized black irregular crystals of Bi8[AlBr4]2.
- Determined the crystal structure: orthorhombic, space group Pna21, isostructural with related halogallates.
- Identified zero-dimensional [Bi8]2+ cluster cations and [AlBr4]- anions.
- Calculations confirmed the electronic stability of the [Bi8]2+ cluster and predicted semiconducting behavior with a 1.51 eV band gap.
Conclusions:
- The synthesis of Bi8[AlBr4]2 demonstrates the effectiveness of Lewis acidic ionic liquids for creating novel bismuth clusters.
- The compound features a stable arachno-type [Bi8]2+ cluster, analogous to known halogallates.
- Bi8[AlBr4]2 is a semiconductor with potential for electronic applications.
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