Li 2BaMgP 2O 8 and Na 2BaMgP 2O 8 were synthesized by a standard solid state reaction. Structural analyses have revealed that Li 2BaMgP 2O 8 is a member of the olgite family, as is the case with Na 2BaMgP 2O 8. The layer-framework build up by corner-sharing MgO 6 octahedra and PO 4 tetrahedra twists around C 3 axes to match the size of B-site cation (Li + or Na +). This twisting affects the coordination number for the B-site cation and unit cell size. Eu-doped Li 2BaMgP 2O 8 and Na 2BaMgP 2O 8 exhibited intense violet-blue emission under ultraviolet excitation. They were characterized by two emission centers; Eu 2 ions replacing A-site cations (Ba 2) and B-site cations (Li + or Na +). The B-site Eu 2 emission was very sensitive to the twisting behavior caused by original B-site cation.
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