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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.
Abstract:
Black irregular crystals of octabismuth(2+) bis(tetrabromidoaluminate), Bi8[AlBr4]2, were synthesized by the reaction of BiBr3, AlBr3, and metallic Bi in a Lewis acidic ionic liquid (LAIL), [BMIm]Br·3.95AlBr3 (BMIm = 1-n-butyl-3-methylimidazolium) at 180 °C via a one-pot reaction. Single-crystal X-ray diffraction analysis showed that the compound crystallizes in the orthorhombic space group Pna21 with unit-cell parameters a = 18.1751 (6), b = 10.2977 (4), and c = 13.4537 (4) Å, and is isostructural with the majority of previously reported halogallates, Pn8[GaX4]2 (Pn = Sb, Bi; X = Cl, Br). The structure consists of distorted square antiprismatic zero-dimensional (0D) [Bi8]2+ cluster cations charge-balanced by tetrahedral [AlBr4]- anions. According to the Wade-Mingos rules, the [Bi8]2+ polycation can be categorized as an arachno-type cluster. Electronic structure calculations performed using molecular and periodic approaches support the electronic stability of the [Bi8]2+ cluster and indicate semiconducting behavior for Bi8[AlBr4]2, with a calculated band gap of 1.51 eV.
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