Evaluation of solution structures of highly luminescent europium(III) chelates by using laser induced excitation of the 7F0 → 5D0 transition
Evaluation of solution structures of highly luminescent europium(III) chelates by using laser induced excitation of the 7F0 → 5D0 transition
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DOI：
10.1016/s0020-1693(97)05553-9
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发表时间：
1998-01
影响因子：
2.8
通讯作者：
M. Latva;H. Takalo;V. Mukkala;J. Kankare
中科院分区：
文献类型：
--
作者：
M. Latva;H. Takalo;V. Mukkala;J. Kankare
通过使用激光诱导激发 7F0→5D0 跃迁来检查 13 Eu(III) 螯合物的溶液结构。根据配体的齿数和配位氮原子的数量和性质，观察到Eu(III)的2,2′,2″,2″−{[芳基]双(亚甲基腈}四(乙酸)配合物的7F0→5D0激发光谱的显着变化。结构的评估是根据Eu(III)的7F0→5Do激发跃迁的能量进行的，因为7F0→5D0 跃迁能量取决于 Eu(III) 第一配位层中配位原子的数量和类型。通过测量 Eu(III) 螯合物的激发态寿命可以获得有关结构的其他信息。由于特定基团或原子的配位，7F0→5D0 跃迁能量总是等量地转移到较低能量。 2,2',2",2"−{[4-苯基乙炔基)吡啶-2,6-二基]双(亚甲基nurido)}四(乙酸)中配位氮杂原子的这些“nephelauxetic”位移参数(3)。 2,2',2",2"-[(2,2'-联吡啶-6,6'-二基)双-(亚甲基次氮基)]四(乙酸)(4)。 2,2′,2″,2″-[(2,2′:6,2″-三联吡啶-6,6″-三联吡啶-6.6″-二基)双(亚甲基次氮基)]四(乙酸)(5),2,2′,2″,2″- (吡唑-1,3-二基)-双(吡啶)-2,2'-二基]双(亚甲基次氮基)]四(乙酸)(7)。 2,2',2",2"-([噻唑-2,4-二基)双(吡啶)-2,2'-二基]-双(亚甲基次氮基(]四(乙酸)) (8) 和2,2',2",2"-([2,2,'-吡啶-2,6-二基)双(噻唑)-4,4'-二基]双-(亚甲基次氮基)]-四(乙酸)(9)配合物。氮杂原子位移参数的变化是由于氮杂原子和Eu(III)离子之间的距离不同造成的。
Solution structures of 13 Eu(III) chelates were examined by using laser induced excitation of the7F0→5D0transition. Remarkable variations in the7F0→5D0excitation spectra of 2,2′,2″,2″−{[aryl]bis(methylenenitrilo}tetrakis(acetic acid) complexes of Eu(III) are observed depending on the denticity of the ligand and the number and character of the coordinated nitrogen atoms. The evaluation of the structures is made on the basis of the energy of the7F0→5Doexcitation transition of Eu(III) because the7F0→5D0transition energy is dependent on the number and type of coordinating atoms in the first coordination sphere of Eu(III). Additional information about the structures is obtained by measuring the excited-state lifetimes of the Eu(III) chelates. The7F0→5D0transition energy shifts always an equal amount to lower energies due to the coordination of a certain group or atom. The energies of the7F0→5D0excitation transitions are also used to calculate these ‘nephelauxetic’ shift parameters for coordinated nitrogen heteroatoms iin the 2,2′,2″,2″−{[4-phenylethynyl)pyridine-2,6-diyl]bis (methylenenurido)}tetrakis(acetic acid) (3). 2,2′,2″,2″-[(2,2′-bipyridine-6,6′-diyl)bis-(methylenenitrilo)] tetrakis (acetic acid) (4). 2,2′,2″,2″-[(2,2′:6,2″-terpyridine-6,6″-terpyridine-6.6″-diyl)bis(methylenenitrilo)]tetrakis(acetic acid) (5), 2,2′,2″,2″- (pyrazole-1,3-diyl)-bis(pyridine)-2,2′-diyl]bis(methylenenitrilo)]tetrakis(acetic acid) (7). 2,2′,2″,2″-([thizole-2,4-diyl)bis(pyridine)- 2,2′-diyl]-bis(methylenenitrilo(]tetrakis(acetic acid) (8) and 2,2′,2″,2″-([2,2,′-pyridine-2,6-diyl)bis(thiazole)-4,4′-diyl]bis-(methylenenitrilo)]-tetrakis(acetic acid) (9) complexes. The variation in the shift parameters of the nitrogen heteroatoms is suggested to be due to the different distances between the nitrogen heteroatoms and Eu(III) ions.