Horniichuk O Y, Kariaka N S, Smola S S, Rusakova N V, Trush V O, Sliva T Y, Amirkhanov V M
Inorganic Chemistry Department, Taras Shevchenko National University of Kyiv, 12, Lva Tolstogo St, Kyiv, 01601, Ukraine.
Lanthanide chemistry department, A. V. Bogatsky Physicochemical Institute of National Academy of Sciences of Ukraine, 86 Lustdorfska doroga, Odesa, 65080, Ukraine.
J Fluoresc. 2021 Jul;31(4):1029-1039. doi: 10.1007/s10895-021-02733-0. Epub 2021 Apr 26.
Binuclear rare earth complexes LnLphen (Ln = Nd, Sm, Eu, Tb, Dy, Yb and Y) with bis-CAPh type ligand - tetramethyl N,N'-(2,2,3,3,4,4-hexafluoro-1,5-dioxopentane-1,5-diyl)bis(phosphoramidate) (HL) and 1,10-phenanthroline (phen) were synthesized and characterized by elemental analysis, IR, NMR, absorption and luminescence spectroscopy. Luminescence measurements were performed for all the complexes in solid state and for the Eu, Tb and Y complexes - in solution in DMSO as well. The effective energy transfer from organic ligands to Ln ions strongly sensitizes the Ln ions emission and under excitation by UV light, the complexes exhibited bright characteristic emission of lanthanide metal centers. It was found that the energy level of the ligands lowest triplet state in the complexes matches better to resonance level of Eu rather than Tb ion. Depending on temperature the emission decay times of solid europium and terbium complexes were in the range of 1.5-2.0 ms. In solid state at room temperature the Eu complex possess intense luminescence with very high intrinsic quantum yield 91% and decay time equal 1.88 ms.
合成了具有双 - CAPh型配体——四甲基N,N'-(2,2,3,3,4,4 - 六氟 - 1,5 - 二氧戊烷 - 1,5 - 二基)双(磷酰胺)(HL)和1,10 - 菲咯啉(phen)的双核稀土配合物LnLphen（Ln = Nd、Sm、Eu、Tb、Dy、Yb和Y），并通过元素分析、红外光谱、核磁共振、吸收光谱和发光光谱对其进行了表征。对所有配合物进行了固态发光测量，对Eu、Tb和Y配合物还在DMSO溶液中进行了发光测量。从有机配体到Ln离子的有效能量转移强烈地敏化了Ln离子的发射，在紫外光激发下，配合物表现出镧系金属中心明亮的特征发射。发现配合物中配体最低三重态的能级与Eu离子的共振能级比与Tb离子的共振能级匹配得更好。根据温度的不同，固态铕和铽配合物的发射衰减时间在1.5 - 2.0毫秒范围内。在室温固态下，Eu配合物具有强烈的发光，其固有量子产率非常高，为91%，衰减时间为1.88毫秒。
