2,2′-bipyridine-6,6′-dicarboxylic acid-D₆ | 1394128-49-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2,2′-bipyridine-6,6′-dicarboxylic acid-D₆
• 英文别名: [D6]-2,2'-bipyridine-6,6'-dicarboxylic acid；[D₆]-2,2'-bipyridine-6,6'-dicarboxylic acid；6-(6-Carboxy-3,4,5-trideuteriopyridin-2-yl)-3,4,5-trideuteriopyridine-2-carboxylic acid；6-(6-carboxy-3,4,5-trideuteriopyridin-2-yl)-3,4,5-trideuteriopyridine-2-carboxylic acid
• CAS: 1394128-49-4
• 化学式: C₁₂H₈N₂O₄
• 分子量: 250.159
• InChiKey: DASAXWLMIWDYLQ-MZWXYZOWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  100
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,2′-bipyridine-6,6′-dicarboxylic acid-D₆ 在 sodium tetrahydroborate 、 硫酸 、 三溴化磷 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 68.0h， 生成 [D₆]-6,6'-bis(bromomethyl)-2,2'-bipyridine
  参考文献：
  名称：

  Anomalous Reversal of C–H and C–D Quenching Efficiencies in Luminescent Praseodymium Cryptates

  摘要：

  A series of selectively deuterated praseodymium cryptates has been synthesized. Their luminescence lifetimes in solution range from 150 to 595 ns for the (1)D(2) → (3)F(4) transition. Global fitting of the nonradiative deactivation rate differences of the isotopologic C-(H/D) oscillators revealed that aromatic C-D overtones anomalously quench the luminescence more than C-H vibrations. This is explained by the dominance of Franck-Condon overlap factors that greatly favor C-D oscillators, which are in almost ideal resonance with the relevant energy gap (1)D(2)-(1)G(4) of praseodymium.

  DOI：

  10.1021/ja306052u
• 作为产物：
  描述：

  [D12]-6,6'-dimethyl-2,2'-bipyridine-N,N'-dioxide 在 chromium(VI) oxide 、 硫酸 、 三溴化磷 作用下， 以 乙腈 为溶剂， 反应 24.0h， 生成 2,2′-bipyridine-6,6′-dicarboxylic acid-D₆
  参考文献：
  名称：

  Anomalous Reversal of C–H and C–D Quenching Efficiencies in Luminescent Praseodymium Cryptates

  摘要：

  A series of selectively deuterated praseodymium cryptates has been synthesized. Their luminescence lifetimes in solution range from 150 to 595 ns for the (1)D(2) → (3)F(4) transition. Global fitting of the nonradiative deactivation rate differences of the isotopologic C-(H/D) oscillators revealed that aromatic C-D overtones anomalously quench the luminescence more than C-H vibrations. This is explained by the dominance of Franck-Condon overlap factors that greatly favor C-D oscillators, which are in almost ideal resonance with the relevant energy gap (1)D(2)-(1)G(4) of praseodymium.

  DOI：

  10.1021/ja306052u

文献信息

• Nonradiative Deactivation of Lanthanoid Excited States by Inner-Sphere Carboxylates
  作者：Jessica Wahsner、Michael Seitz

  DOI：10.1021/acs.inorgchem.5b01920

  日期：2015.11.16

  The vibrational deactivation of metal-centered excited states is one of the fundamental processes that governs the luminescence of inorganic luminophores. In molecular lanthanoid luminescence, the most reliable way to modulate and systematically investigate these processes is deuteration of X–H stretching modes (X = O, N, C). Apart from the effect of these high-energy vibrational motifs, very little

  以金属为中心的激发态的振动失活是控制无机发光体发光的基本过程之一。在分子镧系元素发光中，调节和系统研究这些过程的最可靠方法是氘化X–H拉伸模式（X = O，N，C）。除了这些高能振动基序的影响外，对镧系元素络合物中其他振荡器碎片的影响知之甚少。我们已经开发出一种合成方案，可以稳定地用13 C / 18有效和选择性地标记流行的螯合剂基序“吡啶-2-羧酸”羧基上的O同位素。同位素取代后，相应的同位素镧系元素络合物（Ln = Sm，Eu，Ho）显示出局部模式羰基拉伸频率降低了5％。尽管这似乎对具有中高能隙（Sm和Eu）的镧系元素的发光没有任何影响，但我们发现了for的近红外跃迁中可量化的发光同位素效应的第一个例子（3 K 8 → 5 I 5）仅涉及对四个羰基振荡器处的振动环境进行同位素编辑。
• Breakdown of the Energy Gap Law in Molecular Lanthanoid Luminescence: The Smallest Energy Gap Is Not Universally Relevant for Nonradiative Deactivation
  作者：Christine Doffek、Jessica Wahsner、Elisabeth Kreidt、Michael Seitz

  DOI：10.1021/ic500017a

  日期：2014.4.7

  For several decades, the energy gap law has been the prevalent theoretical framework for the discussion of nonradiative deactivation of lanthanoid luminescence in molecular coordination chemistry. Here we show experimentally on samarium and dysprosium model complexes that the size of the energy gap Delta E between a lanthanoid emitting state and the next-lower electronic state cannot be considered a reliable and accurate predictor of the quantitative extent of nonradiative deactivation by aromatic C-H and C-D oscillator overtones. Because the energy gap is the central pillar for the entire conceptual framework of the energy gap law, this finding amounts to largely invalidating this theory for the quantitative description of molecular multiphonon relaxation.
• Perdeuterated 2,2′-Bipyridine-6,6′-dicarboxylate: An Extremely Efficient Sensitizer for Thulium Luminescence in Solution
  作者：Jessica Wahsner、Michael Seitz

  DOI：10.1021/ic402652t

  日期：2013.12.2

  Lanthanoid luminescence has become an important pillar for many modern photonics applications such as bioanalytical research or functional material science. So far, however, thulium despite having one of the most interesting photophysics among the lanthanoids has suffered from extremely low luminescence efficiencies in molecular complexes with organic sensitizer ligands. This has greatly hampered the investigation and application of thulium emission in solution. Here, the discovery of a powerful sensitizer for thulium photoluminescence is reported. The corresponding thulium complex exhibits emission efficiencies (quantum yield Phi > 0.12%; lifetime tau(obs) = 4.6 mu s; brightness epsilon Phi > 30 M-1 cm(-1)) and can even be detected at low micromolar concentrations in high-phonon solvents like water without the need for laser excitation.
• Anomalous Reversal of C–H and C–D Quenching Efficiencies in Luminescent Praseodymium Cryptates
  作者：Julia Scholten、Geraldine A. Rosser、Jessica Wahsner、Nicola Alzakhem、Caroline Bischof、Felix Stog、Andrew Beeby、Michael Seitz

  DOI：10.1021/ja306052u

  日期：2012.8.29

  A series of selectively deuterated praseodymium cryptates has been synthesized. Their luminescence lifetimes in solution range from 150 to 595 ns for the (1)D(2) → (3)F(4) transition. Global fitting of the nonradiative deactivation rate differences of the isotopologic C-(H/D) oscillators revealed that aromatic C-D overtones anomalously quench the luminescence more than C-H vibrations. This is explained by the dominance of Franck-Condon overlap factors that greatly favor C-D oscillators, which are in almost ideal resonance with the relevant energy gap (1)D(2)-(1)G(4) of praseodymium.