Electrogenerated Chemiluminescence and Electronic States of Several Organometallic Eu(III) and Tb(III) Complexes: Effects of the Ligands
Electrogenerated Chemiluminescence and Electronic States of Several Organometallic Eu(III) and Tb(III) Complexes: Effects of the Ligands
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DOI：
10.1002/slct.201900595
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发表时间：
2019-03-07
期刊：
影响因子：
2.1
通讯作者：
Imato, Toshihiko
中科院分区：
文献类型：
--
作者：
Ishimatsu, Ryoichi;Kunisawa, Eri;Imato, Toshihiko
本文报道了Eu（III）和Tb（III）、Eu(dbm)(3)phen、Eu(dbm)(3)bath、Eu(food)(3)phen、Eu(tta)(3)phen、Tb(acac)(3) phen、Tb(acac)(3)bath、Tb(foc)(3)phen和Tb(tmhd)(3)bpy等八种不同有机金属配合物在乙腈中的电化学性能和电致发光（ECL），其中phen、bath和bpy分别为1,10 -菲罗啉、bathopheno啉、2,2′-联吡啶，以及阴离子配体acac（-）、dbm（-）、food（-）、和tta（-）分别是乙酰丙酮、二苯甲酰甲烷、6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5-辛烷二酮和壬基三氟丙酮的烯醇酯形式。用密度泛函理论计算了配合物的中性电子态和部分带电态。以S(2)O(8)（2-）为反应物记录了ECL光谱，所有配合物的ECL光谱都是由f-f跃迁引起的。在电位依赖的ECL谱上，还检测到来自配体的宽ECL。基于ECL行为和电子态，讨论了构型内ECL的机理。
We report the electrochemical properties, and electrogenerated chemiluminescence (ECL) of eight different organometallic complexes of Eu(III) and Tb(III), Eu(dbm)(3)phen, Eu(dbm)(3)bath, Eu(fod)(3)phen, Eu(tta)(3)phen, Tb(acac)(3)iphen, Tb(acac)(3)bath, Tb (foc)(3)phen, and Tb(tmhd)(3)bpy in acetonitrile, where phen, bath, and bpy are 1, 10-phenanthroline, bathophenanthroline, 2,2'-bipyridyl, respectively, and the anionic ligands, acac(-), dbm(-), fod(-), and tta(-) are the enolate forms of acetylacetone, dibenzoylmethanate, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, and thenoyltrifluoroacetone, respectively. The electronic states of the neutral and some charged states of the complexes were clarified with density functional theory calculations. The ECL spectra were recorded by using S(2)O(8)(2- )as a coreactant, and for all complexes, sharp ECL spectra, which are attributable to the f-f transitions, were observed. On the potential-dependent ECL spectra, broad ECLs, which were originated from the ligands, were also detected. Based on the ECL behavior and the electronic states, the mechanisms of the intraconfigurational ECL were discussed.