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Synthesis in ionic liquids: [Bi2Te2Br](AlCl4), a direct gap semiconductor with a cationic framework.

The Lewis acidic ionic liquid EMIMBr-AlCl(3) (EMIM = 1-ethyl-3-methylimidazolium) allows a novel synthetic route to the semiconducting layered metal chalcogenides halide [Bi(2)Te(2)Br](AlCl(4)) and its Sb analogue. [Bi(2)Te(2)Br](AlCl(4)) is a direct band gap, strongly anisotropic semiconductor and consists of cationic infinite layers of [Bi(2)Te(2)Br](+) and [AlCl(4)](-) anions inserted between the layers.

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