Bi12Rh3Br2: a subbromide from the oxidation of the intermetallic compound Bi4Rh |
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Institution: | 1. Chemical Department, Taras Shevchenko National University of Kyiv, Kyiv, Ukraine;2. G. V. Kurdymov Institute for Metal Physics, Nat. Acad. of Sci. of Ukraine, Ukraine |
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Abstract: | Bi12Rh3Br2 was synthesized from the elements using niobium bromides as auxiliaries to modify the partial pressures in the course of the reaction. The orthorhombic crystal structure (space group Fddd (no. 70); a=717.12(3) pm, b=1680.37(6) pm, c=3187.1(1) pm) consists of a three-dimensional framework of RhBi8] cubes and square antiprisms, which share common edges. Bromide ions fill the chiral pores of the framework. The crystal structure of Bi12Rh3Br2=(Bi4Rh)3Br2 is closely related to that of the intermetallic compound α-Bi4Rh. The oxidation of Bi4Rh to Bi12Rh3Br2 is accompanied by an emptying of BiBi and BiRh antibonding states near the Fermi level, leading to a strengthening of bonding in the intermetallic part of the structure. Despite the partial oxidation the metallic conductivity is retained. |
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