N-(4,6-dimethyl-2-oxochromen-7-yl)-N-ethyl-2-(1,4,7,10-tetrazacyclododec-1-yl)acetamide | 947702-67-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: N-(4,6-dimethyl-2-oxochromen-7-yl)-N-ethyl-2-(1,4,7,10-tetrazacyclododec-1-yl)acetamide
• CAS: 947702-67-2
• 化学式: C₂₃H₃₅N₅O₃
• 分子量: 429.563
• InChiKey: BRIBKESHKZHVBD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  85.9
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  N-(4,6-dimethyl-2-oxochromen-7-yl)-N-ethyl-2-(1,4,7,10-tetrazacyclododec-1-yl)acetamide 在 sodium carbonate 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 16.0h， 生成 (x)C₂HF₃O₂*C₂₉H₄₁N₅O₉
  参考文献：
  名称：

  Synthesis and photophysical characterization of luminescent lanthanide complexes of nucleotide-functionalized cyclen- and dipicolinate-based ligands

  摘要：

  Luminescent Eu(III)-and Tb(III)-complexes based on functionalized tetraazamacrocycle (cyclen) or dipicolinic acid (dpa) metal binding sites, and carrying 20-or 50-linked uridine moieties were prepared. The light-harvesting antennae were either a coumarin (in the cyclen-based architectures) or the dpa-moiety itself. Antenna excitation resulted in metal-centered emission for all complexes. The presence of the uridine resulted in less intense lanthanide emission compared to non-nucleotide-modified reference compounds. Nd(III)-complexes of cyclen ligands carrying a uridine but without a sensitizing antenna were also synthesized; these are envisioned as energy transfer acceptors to the Eu(III)-complexes. The possibility for Eu-to-Nd energy transfer was probed. The reported complexes are models for oligonucleotide- attached lanthanide probes. (C) 2016 The Author(s). Published by Elsevier B.V.

  DOI：

  10.1016/j.ica.2016.07.047
• 作为产物：
  描述：

  2-bromo-N-(4,6-dimethyl-2-oxochromen-7-yl)-N-ethylacetamide 、 轮环藤宁 在 三乙胺 作用下， 以 乙醇 为溶剂， 反应 24.0h， 生成 N-(4,6-dimethyl-2-oxochromen-7-yl)-N-ethyl-2-(1,4,7,10-tetrazacyclododec-1-yl)acetamide
  参考文献：
  名称：

  Near IR-emitting DNA-probes exploiting stepwise energy transfer processes

  摘要：

  报告了两种新的基于环烯的近红外发光镧系配合物的合成和表征；这些镧系元素由罗丹明激发，而罗丹明又由香豆素 2 分子的能量转移激发。这三种发光体在光谱的紫外-可见-近红外区域发挥着能量转移级联的作用，从而产生巨大的斯托克斯偏移。双股 DNA 可选择性地关闭两个能量转移过程中的一个，从而实现近红外区域的 DNA 发光传感。DFT 计算解释了环烯支架的区域选择性二烷基化。

  DOI：

  10.1039/b708940f

文献信息

• Synthesis of asymmetrically substituted cyclen-based ligands for the controlled sensitisation of lanthanides
  作者：K. Eszter Borbas、James I. Bruce

  DOI：10.1039/b705757a

  日期：——

  A series of unsymmetrical cyclen-based ligands incorporating an antenna and a quencher have been prepared for the complexation of the visible- (Eu, Tb) and near IR-emitting (Nd, Yb) lanthanides. Eu and Tb were sensitised with coumarin 2, and Nd and Yb with rhodamine. Both antennae were paired with nucleoside (uridine and adenosine) quenchers. The interaction between the quencher and the antenna can be regulated by the addition of the complementary base or DNA to the complexes, resulting in changes in the lanthanide luminescence intensity and lifetime.

  一系列不对称的基于环的配体被制备，以结合可见光（Eu，Tb）和近红外发射（Nd，Yb）的锕系元素。这些配体中，Eu和Tb与香豆素2进行敏化，而Nd和Yb则与罗丹明结合。两个天线都与核苷（尿苷和腺苷）熄灭剂配对。通过向复合物中添加互补碱基或DNA，可以调节熄灭剂与天线之间的相互作用，从而导致锕系元素的发光强度和寿命发生变化。
• Photophysics of Coumarin and Carbostyril-Sensitized Luminescent Lanthanide Complexes: Implications for Complex Design in Multiplex Detection
  作者：Daniel Kovacs、Xi Lu、Lívia S. Mészáros、Marjam Ott、Julien Andres、K. Eszter Borbas

  DOI：10.1021/jacs.6b11274

  日期：2017.4.26

  Luminescent lanthanide (Ln(III)) complexes with coumarin or carbostyril antennae were synthesized and their photophysical properties evaluated using steady-state and time-resolved UV-vis spectroscopy. Ligands bearing distant hydroxycoumarin-derived antennae attached through triazole linkers were modest sensitizers for Eu(III) and Tb(III), whereas ligands with 7-amidocarbostyrils directly linked to the coordination site could reach good quantum yields for multiple Ln(III), including the visible emitters Sm(III) and Dy(III), and the near-infrared emitters Nd(III) and Yb(III). The highest lanthanide-centered luminescence quantum yields were 35% (Tb), 7.9% (Eu), 0.67% (Dy), and 0.18% (Sm). Antennae providing similar luminescence intensities with 2-4 Ln-emitters were identified. Photoredox quenching of the carbostyril antenna excited states was observed for all Eu(III)-complexes and should be sensitizing in the case of Yb(III); the scope of the process extends to Ln(III) for which it has not been seen previously, specifically Dy(III) and Sm(III). The proposed process is supported by photophysical and electrochemical data. A FRET-type mechanism was identified in architectures with both distant and close antennae for all of the Lns. This mechanism seems to be the only sensitizing one at long distance and probably contributes to the sensitization at shorter distances along with the triplet pathway. The complexes were nontoxic to either bacterial or mammalian cells. Complexes of an ester-functionalized ligand were taken up by bacteria in a concentration-dependent manner. Our results suggest that the effects of FRET and photoredox quenching should be taken into consideration when designing luminescent Ln complexes. These results also establish these Ln(III)-complexes for multiplex detection beyond the available two-color systems.