Einkauf Jeffrey D, Kelley Tanya T, Chan Benny C, de Lill Daniel T
Department of Chemistry & Biochemistry, Florida Atlantic University , 777 Glades Road, Boca Raton, Florida 33431 United States.
Department of Chemistry, The College of New Jersey , 2000 Pennington Road, Ewing, New Jersey 08628, United States.
Inorg Chem. 2016 Aug 15;55(16):7920-7. doi: 10.1021/acs.inorgchem.6b00878. Epub 2016 Jul 29.
A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.
合成并表征了一种由二苯甲酮二羧酸酯组装而成的配位聚合物[Ln(C₁₅H₉O₉)₃(H₂O)₃]ₙ（1-Ln = Eu(III)，Tb(III)）。结果表明，有机组分在这两种化合物中均能敏化基于镧系元素的发光，量子产率分别为36%（Eu）和6%（Tb）。目前从分子角度描述镧系配位聚合物的发光。这种方法无法解释该体系的发光现象。研究发现，有机组分的能带结构而非分子三重态能够解释观察到的发光现象。还研究了氘代（Ln(C₁₅H₉O₉)₃(D₂O)₃）和脱水（Ln(C₁₅H₉O₉)₃）类似物。当结合的H₂O被D₂O取代时，寿命和发射如预期那样增加。脱水后，寿命再次增加，但1-Eu的发射意外降低。这种降低是通过有机到Eu(III)能量转移过程中OH/OD振荡器对化合物发光的前所未有的增强效应来解释的。
