We report on the structure and luminescence of a double salt trivalent rare earth ion acceptor, Tb 3+ , with octahedral [BiCl 6 ] 3– donor clusters. The novel TbBiCl 6 •14H 2 O (1) was prepared from aqueous BiOCl and TbCl 3 •6H 2 O. The crystal structure of compound 1 exhibits isolated [BiCl 6 ] 3– and [Tb(OH 2 ) 8 ] 3+ clusters. Luminescence data show energy transfer from octahedral chlorobismuthate(III) clusters to rare earth metal ions. Density Functional Theory (DFT) calculations show distinctly different emission pathways at high and low excitation energies.
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