探索金属有机框架中的镧系元素发光：一种铕/铽混合己二酸酯框架和一种铽己二酸酯框架的合成、结构及客体敏化发光
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.
作者信息
de Lill Daniel T, de Bettencourt-Dias Ana, Cahill Christopher L
机构信息
Department of Chemistry, The George Washington University, 725 21st Street, NW, Washington, DC 20052, USA.
出版信息
Inorg Chem. 2007 May 14;46(10):3960-5. doi: 10.1021/ic062019u. Epub 2007 Apr 18.
Two lanthanide-organic frameworks were synthesized via hydrothermal methods. Compound 1 ([(Eu,Tb)(C6H8O4)3(H2O)2].(C10H8N2), orthorhombic, Pbcn, a = 21.925(2) A, b = 7.6493(7) A, c = 19.6691(15) A, alpha = beta = gamma = 90 degrees, Z = 4) takes advantage of the similar ionic radii of the lanthanide elements to induce a mixed-lanthanide composition. Compound 2 ([Tb2(C6H8O4)3(H2O)2].(C10H8N2), orthorhombic, Pbcn, a = 21.866(3) A, b = 7.6101(10) A, c = 19.646(3) A, alpha = beta = gamma = 90 degrees, Z = 8) is the terbium-only analogue of compound 1. Solid-state measurements of their luminescence behavior demonstrate that the neutral guest molecule (4,4'-dipyridyl) residing in the extraframework channels is successful in sensitizing lanthanide ion emission. In compound 1, columinescence occurs, and both lanthanide ions show emission. Additionally, quantum yield and lifetime measurements support the premise that the Tb3+ center is also acting to sensitize the Eu3+, effectively enhancing Eu3+ emission.
通过水热法合成了两种镧系有机框架化合物。化合物1（[(Eu,Tb)(C6H8O4)3(H2O)2].(C10H8N2)，正交晶系，Pbcn空间群，a = 21.925(2) Å，b = 7.6493(7) Å，c = 19.6691(15) Å，α = β = γ = 90°，Z = 4）利用镧系元素相似的离子半径诱导形成混合镧系组成。化合物2（[Tb2(C6H8O4)3(H2O)2].(C10H8N2)，正交晶系，Pbcn空间群，a = 21.866(3) Å，b = 7.6101(10) Å，c = 19.646(3) Å，α = β = γ = 90°，Z = 8）是化合物1的仅含铽的类似物。对它们发光行为的固态测量表明，位于骨架外通道中的中性客体分子（4,4'-联吡啶）成功地敏化了镧系离子发射。在化合物1中，发生共发光，两种镧系离子均有发射。此外，量子产率和寿命测量支持了Tb3+中心也在敏化Eu3+这一前提，有效地增强了Eu3+的发射。
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