Exploring Lanthanide Luminescence in Metal-Organic Frameworks: Synthesis, Structure, and Guest-Sensitized Luminescence of a Mixed Europium/Terbium-Adipate Framework and a Terbium-Adipate Framework
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Two lanthanide-org. frameworks were synthesized via hydrothermal methods. Compd. (1) ([(Eu,Tb)(C6H8O4)3(H2O)2].bul.(C10H8N2), orthorhombic, space group Pbcn, a 21.925(2), b 7.6493(7), c 19.6691(15) .ANG., a = b = g 90. Deg, Z = 4) takes advantage of the similar ionic radii of the lanthanide elements to induce a mixed-lanthanide compn. Compd. (2) ([Tb2(C6H8O4)3(H2O)2].bul.(C10H8N2), orthorhombic, space group Pbcn, a 21.866(3), b 7.6101(10), c 19.646(3) .ANG., a = b = g 90. Deg, Z = 8) is the Tb-only analog of 1. Solid-state measurements of their luminescence behavior demonstrate that the neutral guest mol. (4,4'-dipyridyl) residing in the extra framework channels is successful in sensitizing lanthanide ion emission. In compd. 1, co-luminescence occurs, and both lanthanide ions show emission. Addnl., quantum yield and lifetime measurements support the premise that the Tb3+ center is also acting to sensitize the Eu3+, effectively enhancing Eu3+ emission.