Tb(2,6-pyridinedicarboxylate)(3-) | 38682-37-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Tb(2,6-pyridinedicarboxylate)(3-)
• 英文别名: [Tb(2,6-pyridinedicarboxylate)3](3-)；[Tb(pyridine-2,6-dicarboxylate)3](3-)；[Tb(dipicolate)3](3-)；Pyridine-2,6-dicarboxylate;terbium(3+)
• CAS: 38682-37-0
• 化学式: C₂₁H₉N₃O₁₂Tb
• 分子量: 654.241
• InChiKey: YOYQTHIHEJVFSO-UHFFFAOYSA-H

计算性质

• 辛醇/水分配系数(LogP)：
  -6.57
• 重原子数：
  37
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  279
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  D-allose 、 Tb(2,6-pyridinedicarboxylate)(3-) 以 水 为溶剂， 生成 tris(pyridine-2,6-dicarboxylato)terbate(III)(3-)*D-allose
  参考文献：
  名称：

  单糖醛糖在三（吡啶-2,6-二羧基戊酸）三（三吡啶）中诱导的菲佛效应的研究

  摘要：

  在与单糖醛糖形成外球络合物后，在[Tb（pydca）3 ] 3–（pydca =吡啶-2,6-二羧酸吡啶）的外消旋混合物中诱导了光学活性，并通过圆偏振发光光谱法对其进行了研究。将D-甘油醛添加到[Tb（pydca）3 ] 3–的溶液中未观察到光学活性，这表明存在半缩醛环氧是发生外球缔合所必需的。发现诱导的光学活性的符号随所用糖的身份而变化，但是在糖的碳原子4（当它们以吡喃糖环形式存在时）的构型与主要的[Tb（ pydca）3 ] 3–对映异构体。这表明缔合过程确实导致了观察到的菲佛效应，并且导致形成外圈复合物的力在本质上是相当特殊的。

  DOI：

  10.1039/dt9840001367
• 作为产物：
  描述：

  吡啶-2,6-二甲酸 、 terbium(III) carbonate 以 水 为溶剂， 生成 Tb(2,6-pyridinedicarboxylate)(3-)
  参考文献：
  名称：

  溶液中不对称金属配合物之间电子能量转移过程的手性鉴别。对映选择性激发态猝灭动力学的时间分辨手性发光测量

  摘要：

  稳态和时间分辨手性发光测量用于研究溶液中的对映选择性激发态猝灭过程。理论和测量方法是针对手性发光体的初始外消旋激发态群体在手性猝灭剂分子存在下演变为非外消旋群体的情况提出的。在发光体激发态群体中产生对映体过量产生左右圆偏振光的差异（自发）发射，并且这种手性发光的时间依赖性提供了与同手性与异手性相关的差异激发态猝灭动力学的直接测量发光体-猝灭剂相互作用。

  DOI：

  10.1021/ja00171a001

文献信息

• Chiral discrimination in electronic energy-transfer processes in solution. Effects of temperature and solution properties on chirality-dependent rate parameters
  作者：Deborah P. Glover-Fischer、David H. Metcalf、James P. Bolender、F.S. Richardson

  DOI：10.1016/0301-0104(95)00173-l

  日期：1995.9

  Time-resolved chiroptical luminescence (TR-CL) measurements are used to study the kinetics of chilality-dependent excited-state quenching processes in solution. Solution samples contain a racemic mixture of chiral luminophore molecules (L) and a small, optically-resolved concentration of chiral quencher molecules (Q) in an achiral solvent (H2O, D2O, or an H2O-ethylene glycol mixture). The luminophores

  时间分辨的手性发光（TR-CL）测量用于研究溶液中手性相关的激发态猝灭过程的动力学。溶液样品包含手性发光体分子（L）的外消旋混合物和非手性溶剂（H 2 O，D 2 O或H 2 O-乙二醇混合物中的少量光学拆分的手性淬灭剂分子（Q））。用非偏振光脉冲激发发光体，以产生初始外消旋的ΔL ∗和ΛL ∗对映体的激发态团簇，然后使用TR-CL测量来监测ΔL ∗和ΛL ∗的微分衰减动力学。亚群。观察到ΔL ∗和ΛL ∗衰减动力学差分速率过程之间的差异以及ΔL ∗ -Q与ΛL ∗ -Q猝灭作用的效率之间的差异，它们可诊断发光体和猝灭剂分子之间的手性区分性相互作用。在这里检查的每个系统中，淬灭都是通过电子能量传递过程在瞬态（ΔL ∗ -Q）和（ΛL ∗-Q）遇到配合物，并且手性鉴别率参数反映了这些配合物的相对稳定性和寿命，以及它们的结构和内部（电子和核）动力学。在本研究表示的温度范围内，淬火速率和对映选择性都随温度的升高而增加（H
• Analysis of Paramagnetic NMR Spectra of Triple-Helical Lanthanide Complexes with 2,6-Dipicolinic Acid Revisited:  A New Assignment of Structural Changes and Crystal-Field Effects 25 Years Later
  作者：Nadjet Ouali、Bernard Bocquet、Stéphane Rigault、Pierre-Yves Morgantini、Jacques Weber、Claude Piguet

  DOI：10.1021/ic010801i

  日期：2002.3.1

  6-dicarboxylic acid) shows that fast intramolecular P <==> M interconversion between the helical enantiomers occurs on the NMR time scale. Detailed analyses of the paramagnetic NMR hyperfine shifts according to crystal-field independent techniques demonstrate the existence of two different helical structures, one for large lanthanides (Ln = La-Eu) and one for small lanthanides (Ln = Tb-Lu), in complete contrast

  D（3）-对称三螺旋络合物[Ln（L1-2H）（3）]（3）（-）的（1）H和（13）C NMR可变温度测量（L1 =吡啶-2， 6-二羧酸； Ln = La-Lu）显示了动态分子间配体交换过程的证据，其活化能取决于金属离子的大小。在298 K时，在[Ln（L3-2H）（3）]（3）（-）（L3 = 4-乙基吡啶-2,6-二羧酸）中使用非对映探针显示快速分子内P <= =>螺旋对映异构体之间的M互变发生在NMR时间尺度上。根据独立于晶体场的技术对顺磁NMR超精细位移的详细分析表明，存在两种不同的螺旋结构，一种为大镧系元素（Ln = La-Eu），一种为小镧系元素（Ln = Tb-Lu），与25年前提出的同构性完全相反。仔细考虑原始晶体场相关的分析表明，轴向晶体场参数A（0）2的突然变化平行于结构变化会导致一些偶然的补偿效果，从而阻止根据经典的单核方法检测结构变化。固态的晶体结构和气相的密度
• Thermodynamics of the enantioselective quenching of tris(2,6-pyridinedicarboxylate)terbate(3-) luminescence by resolved tris(1,10-phenanthroline)ruthenium(2+)
  作者：Roel B. Rexwinkel、Stefan C. J. Meskers、James P. Riehl、Harry P. J. M. Dekkers

  DOI：10.1021/j100117a039

  日期：1993.4

  The temperature dependence of the enantioselective quenching of racemic (DELTA,LAMBDA)-Tb(DPA)3(3-) (DPA = 2,6-pyridinedicarboxylate) by DELTA-Ru(1,10-phenanthroline)3(2+) in H2O,D2O, and methanol is reported. Rate constants for the two diastereomeric quenching reactions may be determined from a nonlinear least-squares fit of the decay of the total luminescence from excited Tb(DPA)3(3-). Analysis of the biexponential decay data in water (5-80-degrees-C) indicates that the kinetics of the quenching reactions can be accurately described as a preequilibrium between isolated donor and quencher species and an associated ion pair, followed by energy transfer to the acceptor. In methanol a wider temperature range (-85 to 50-degrees-C) can be studied, and it is demonstrated that, dependent on solution ionic strength, at high temperatures the preequilibrium limit is appropriate, but at the lowest temperatures studied, the quenching reactions become entirely diffusion controlled, and the enantioselectivity vanishes. In all three solvents at the higher temperatures the overall quenching reactions are associated with negative activation energies. All of the quenching reactions may be analyzed within activated complex theory to yield activation energies, enthalpies, and free energies for the diastereomeric reaction schemes in both solvents. In addition, the temperature dependence of the equilibrium constant for ion-pair association has been determined. From all of these data, it is concluded that, based on enthalpy considerations, the quenching of like enantiomers (DELTA-DELTA, homochiral quenching) is larger than the quenching of unlike enantiomers (LAMBDA-DELTA, heterochiral quenching) but that entropy considerations favor the reverse preference. These generalizations are used to explain the observed differences in enantioselectivity observed in methanol and water.
• Analysis of enantioselective quenching of tris(2,6-pyridinedicarboxylate)terbate(3-) luminescence by resolved tris(1,10-phenanthroline)ruthenium(2+) in methanol and in water
  作者：Roel B. Rexwinkel、Stefan C. J. Meskers、James P. Riehl、Harry P. J. M. Dekkers

  DOI：10.1021/j100182a018

  日期：1992.2

  Circularly polarized luminescence is observed from racemic solutions of Tb(2,6-pyridinedicarboxylate)3(3-) when small amounts of resolved Ru(1,10-phenanthroline)3(2+) are added. This phenomenon has been attributed to enantioselective quenching of the terbium complex by the ruthenium species, resulting in a nonracemic excited-state population. In this work, a simple kinetic scheme for this quenching process is presented, and it is demonstrated that the individual diastereomeric rate constants may be determined directly through numerical fitting of the biexponential decay of the total luminescence intensity. This is shown to give essentially the same results as numerical fitting of the time decay of the luminescence dissymmetry factor when data from both of these measurement techniques are available. It is also demonstrated that the enantioselectivity in the chiral quenching is solvent dependent. In aqueous solutions, for example, addition of DELTA-(-)-Ru(phen)3(2+) results in an excess of DELTA-Tb(DPA)3(3-), i.e., the DELTA enantiomer is quenched more efficiently, whereas in methanol the opposite enantiomer is in excess.
• Metcalf, David H.; Stewart, John M. McD.; Snyder, Seth W., Inorganic Chemistry, 1992, vol. 31, # 12, p. 2445 - 2455
  作者：Metcalf, David H.、Stewart, John M. McD.、Snyder, Seth W.、Grisham, Charles M.、Richardson

  DOI：——

  日期：——