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Aspects of lanthanide complexes for selectivity, intensity and sharpness in luminescence bands from twenty-four praseodymium, europium and gadolinium complexes with differently distorted-hexadentate ligands.
Photochemical & Photobiological Sciences ( IF 2.7 ) Pub Date : 2020-06-12 , DOI: 10.1039/d0pp00069h Miki Hasegawa 1, 2 , Shoya Sakurai 1 , Masafumi Andrew Yamaguchi 1 , Daichi Iwasawa 1 , Naho Yajima 1 , Shuhei Ogata 1 , Yudai Inazuka 1 , Ayumi Ishii 2, 3, 4 , Kengo Suzuki 5
Photochemical & Photobiological Sciences ( IF 2.7 ) Pub Date : 2020-06-12 , DOI: 10.1039/d0pp00069h Miki Hasegawa 1, 2 , Shoya Sakurai 1 , Masafumi Andrew Yamaguchi 1 , Daichi Iwasawa 1 , Naho Yajima 1 , Shuhei Ogata 1 , Yudai Inazuka 1 , Ayumi Ishii 2, 3, 4 , Kengo Suzuki 5
Affiliation
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We structurally and spectroscopically investigated a series of praseodymium (Pr) complexes with eight ligands that form helicate molecular structures. The mother ligand skeleton (L) has two bipyridine moieties bridged with ethylenediamine. The bridged skeleton of PrL was changed to diamines 1-methyl-ethylenediamine, trimethylenediamine and 2,2′-dimethyl-trimethylenediamine, and the corresponding ligands were designated as Lme, Lpr and Ldmpr, for each Pr in these complexes upon UV-excitation. The luminescence quantum yields of PrL and PrLpr in the visible and near infrared (NIR) regions indicate that PrL is excited by both the electronic state of the ligand and the ff absorption band, whereas PrLpr is excited through the ligand. The addition of a methyl group to PrL and PrLpr has a different effect on the Pr emission intensity with the intensity of PrLme decreasing more than that of PrL and PrLdmpr and increasing more than that of PrLpr. Thus, the coordination of Pr and the increased rigidity of the ligand upon methylation enhance luminescence. The azomethine moieties on Lme, Lpr and Ldmpr were reduced and formed the corresponding PrLH, PrLmeH, PrLprH and PrLdmprH complexes. The luminescence of the non-methylated series is due to transitions related to the 1D2 level and thus the methylated series luminesces due to high energy levels such as 3PJ arising from the shortened π electronic systems. We also discuss the strong red emission of a series of Eu complexes with eight ligands from the viewpoint of their molecular structures and luminescence efficiencies and evaluate the Judd–Ofelt parameters from the luminescence spectra of Eu complexes.
中文翻译：
镧系元素络合物在二十四个，六齿配体不同的发光ase 、,和g络合物的发光带中的选择性，强度和清晰度。
我们在结构上和光谱上研究了一系列带有八个配体的lic（Pr）配合物，这些配体形成了螺旋状分子结构。母体配体骨架（L）具有两个联有乙二胺的联吡啶部分。PrL的桥接骨架被更改为二胺1-甲基-乙二胺，三亚甲基二胺和2,2'-二甲基-三亚甲基二胺，相应的配体被命名为L me，L pr和L dmpr，这些复合物中的每个Pr在紫外光下-励磁。PrL和PrL pr在可见光和近红外（NIR）区域的发光量子产率表明PrL被配体的电子状态和ff吸收带所激发，而PrL pr通过配体被激发。在PrL和PrL pr中添加甲基对Pr发射强度有不同的影响，PrL me的强度下降程度要比PrL和PrL dmpr的下降幅度大，而PrL pr的强度则上升幅度更大。因此，Pr的配位和甲基化后配体刚性的提高增强了发光。L me，L pr和L dmpr上的偶氮甲碱部分被还原并形成相应的PrLH，PrL me H，PrL pr H和PrL dmpr H复合物。非甲基化系列的发光是由于与1相关的跃迁由于高能级（例如3 P J）的缩短，π电子系统产生了D 2能级，从而使甲基化系列发光体发光。我们还从分子结构和发光效率的角度讨论了具有八个配体的一系列Eu配合物的强红色发射，并从Eu配合物的发光光谱评估了Judd-Ofelt参数。
更新日期：2020-08-12
中文翻译：
镧系元素络合物在二十四个，六齿配体不同的发光ase 、,和g络合物的发光带中的选择性，强度和清晰度。
我们在结构上和光谱上研究了一系列带有八个配体的lic（Pr）配合物，这些配体形成了螺旋状分子结构。母体配体骨架（L）具有两个联有乙二胺的联吡啶部分。PrL的桥接骨架被更改为二胺1-甲基-乙二胺，三亚甲基二胺和2,2'-二甲基-三亚甲基二胺，相应的配体被命名为L me，L pr和L dmpr，这些复合物中的每个Pr在紫外光下-励磁。PrL和PrL pr在可见光和近红外（NIR）区域的发光量子产率表明PrL被配体的电子状态和ff吸收带所激发，而PrL pr通过配体被激发。在PrL和PrL pr中添加甲基对Pr发射强度有不同的影响，PrL me的强度下降程度要比PrL和PrL dmpr的下降幅度大，而PrL pr的强度则上升幅度更大。因此，Pr的配位和甲基化后配体刚性的提高增强了发光。L me，L pr和L dmpr上的偶氮甲碱部分被还原并形成相应的PrLH，PrL me H，PrL pr H和PrL dmpr H复合物。非甲基化系列的发光是由于与1相关的跃迁由于高能级（例如3 P J）的缩短，π电子系统产生了D 2能级，从而使甲基化系列发光体发光。我们还从分子结构和发光效率的角度讨论了具有八个配体的一系列Eu配合物的强红色发射，并从Eu配合物的发光光谱评估了Judd-Ofelt参数。
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