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Powder X-ray diffraction as well as micro-Raman scattering results revealed that, in addition to crystalline Bi5(GaCl4)3 in the product, amorphous phase containing [GaCl4]- and [Ga2Cl7]- units also exist. The thorough comparison of steady-state and time-resolved photoluminescent behaviors between Bi5(GaCl4)3 product and Bi5(AlCl4)3 crystal leads us to conclude that Bi53+ is the dominant emitter in the product, which gives rise to the ultrabroad emission ranging from 1 to 2.7 micrometer. 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