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Tripyridinophane Platform Containing Three Acetate Pendant Arms: An Attractive Structural Entry for the Development of Neutral Eu(III) and Tb(III) Complexes in Aqueous Solution.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-01-08 , DOI: 10.1021/acs.inorgchem.9b03345 Nadine Leygue 1 , Chantal Galaup 1 , Alberto Lopera 2 , Estefanía Delgado-Pinar 2 , René M Williams 3 , Heinz Gornitzka 4 , Jurriaan M Zwier 5 , Enrique García-España 2 , Laurent Lamarque 5 , Claude Picard 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-01-08 , DOI: 10.1021/acs.inorgchem.9b03345 Nadine Leygue 1 , Chantal Galaup 1 , Alberto Lopera 2 , Estefanía Delgado-Pinar 2 , René M Williams 3 , Heinz Gornitzka 4 , Jurriaan M Zwier 5 , Enrique García-España 2 , Laurent Lamarque 5 , Claude Picard 1
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We report a detailed characterization of Eu3+ and Tb3+ complexes derived from a tripyridinophane macrocycle bearing three acetate side arms (H3tpptac). Tpptac3- displays an overall basicity (∑ log KiH) of 24.5, provides the formation of mononuclear ML species, and shows a good binding affinity for Ln3+ (log KLnL = 17.5-18.7). These complexes are also thermodynamically stable at physiological pH (pEu = 18.6, pTb = 18.0). It should be noted that the pGd value of Gd-tpptac (18.4) is only slightly lower than that of commercially available MRI contrast agents such as Gd-dota (pGd = 19.2). Moreover, a very good selectivity for these ions over the endogenous cations (log KCuL = 14.4, log KZnL = 12.9, and log KCaL = 9.3) is observed. The X-ray structure of the terbium complex shows the metal coordinated by the nine N6O3 donor set of the ligand and one inner-sphere water molecule. DFT calculations result in two Eu-tpptac structures with similar bond energies (ΔE = 0.145 eV): one structure in which the water is coordinated to the metal ion and one structure in which the water molecule is farther away from the ion, bound to the ligand with an OH-π bond. By detailed luminescence experiments, we demonstrate that the europium complex in aqueous solution presents a hydration equilibrium between nine-coordinate, dehydrated [Eu-tpptac]0 and ten-coordinate, monohydrated [Eu-tpptac(H2O)]0 species. A similar trend is observed for the terbium complex. Despite the presence of this hydration equilibrium, the H3tpptac ligand sensitizes Eu3+ and Tb3+ luminescence efficiently in buffered water at physiological pH. Particularly, the terbium complex displays a long excited-state lifetime of 2.24 ms and an overall quantum yield of 33% with a brightness of 3600 M-1 cm-1. Such features of Ln3+ complexes of H3tpptac indicate that this platform appears to be particularly appealing for the further development of luminescent lanthanide labels.
中文翻译：
含有三个乙酸酯垂体臂的三甲吡啶烷平台：用于在水溶液中形成中性Eu（III）和Tb（III）配合物的有吸引力的结构入口。
我们报告了详细的表征Eu3 +和Tb3 +配合物，该配合物衍生自带有三个乙酸酯侧臂（H3tpptac）的三甲in环大环。Tpptac3-的总体碱度（∑ log KiH）为24.5，形成单核ML物种，并且对Ln3 +具有良好的结合亲和力（log KLnL = 17.5-18.7）。这些复合物在生理pH下也具有热力学稳定性（pEu = 18.6，pTb = 18.0）。应该注意的是，Gd-tpptac的pGd值（18.4）仅略低于诸如Gd-dota之类的市售MRI造影剂（pGd = 19.2）。此外，观察到这些离子对内源阳离子的选择性非常好（log KCuL = 14.4，log KZnL = 12.9，log KCaL = 9.3）。complex配合物的X射线结构显示金属由配体的9个N6O3供体组和一个内球水分子配位。DFT计算得出两种具有相似键能（ΔE= 0.145 eV）的Eu-tpptac结构：一种结构中的水与金属离子配位，另一种结构中的水分子远离离子，与金属离子结合具有OH-π键的配体。通过详细的发光实验，我们证明了水溶液中的complex络合物在九配位的脱水[Eu-tpptac] 0和十配位的一水合[Eu-tpptac（H2O）] 0物种之间呈现水合平衡。对于complex络合物观察到类似的趋势。尽管存在这种水合平衡，H3tpptac配体可在生理pH值的缓冲水中有效地敏化Eu3 +和Tb3 +发光。特别地，b络合物显示出2.24 ms的长激发态寿命，总量子产率为33％，亮度为3600 M-1 cm-1。H3tpptac的Ln3 +配合物的此类特征表明，该平台似乎对发光镧系元素标记的进一步发展特别有吸引力。
更新日期：2020-01-08
中文翻译：
含有三个乙酸酯垂体臂的三甲吡啶烷平台：用于在水溶液中形成中性Eu（III）和Tb（III）配合物的有吸引力的结构入口。
我们报告了详细的表征Eu3 +和Tb3 +配合物，该配合物衍生自带有三个乙酸酯侧臂（H3tpptac）的三甲in环大环。Tpptac3-的总体碱度（∑ log KiH）为24.5，形成单核ML物种，并且对Ln3 +具有良好的结合亲和力（log KLnL = 17.5-18.7）。这些复合物在生理pH下也具有热力学稳定性（pEu = 18.6，pTb = 18.0）。应该注意的是，Gd-tpptac的pGd值（18.4）仅略低于诸如Gd-dota之类的市售MRI造影剂（pGd = 19.2）。此外，观察到这些离子对内源阳离子的选择性非常好（log KCuL = 14.4，log KZnL = 12.9，log KCaL = 9.3）。complex配合物的X射线结构显示金属由配体的9个N6O3供体组和一个内球水分子配位。DFT计算得出两种具有相似键能（ΔE= 0.145 eV）的Eu-tpptac结构：一种结构中的水与金属离子配位，另一种结构中的水分子远离离子，与金属离子结合具有OH-π键的配体。通过详细的发光实验，我们证明了水溶液中的complex络合物在九配位的脱水[Eu-tpptac] 0和十配位的一水合[Eu-tpptac（H2O）] 0物种之间呈现水合平衡。对于complex络合物观察到类似的趋势。尽管存在这种水合平衡，H3tpptac配体可在生理pH值的缓冲水中有效地敏化Eu3 +和Tb3 +发光。特别地，b络合物显示出2.24 ms的长激发态寿命，总量子产率为33％，亮度为3600 M-1 cm-1。H3tpptac的Ln3 +配合物的此类特征表明，该平台似乎对发光镧系元素标记的进一步发展特别有吸引力。
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