4-(di(2-picolyl)aminomethyl)-1,10-phenanthroline | 1345842-95-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 4-(di(2-picolyl)aminomethyl)-1,10-phenanthroline
• 英文别名: 1-(1,10-phenanthrolin-4-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine
• CAS: 1345842-95-6
• 化学式: C₂₅H₂₁N₅
• 分子量: 391.475
• InChiKey: BGLIIVVKTKSVDT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  54.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ammonium hexafluorophosphate 、 [(2-(2,4-di(trifluoromethyl)phenyl)-pyridinate)2Ir(μ-Cl)]2 、 4-(di(2-picolyl)aminomethyl)-1,10-phenanthroline 以 二氯甲烷 为溶剂， 反应 18.0h， 生成
  参考文献：
  名称：

  Synthetic Control Over Photoinduced Electron Transfer in Phosphorescence Zinc Sensors

  摘要：

  Despite the promising photofunctionalities, phosphorescent probes have been examined only to a limited extent, and the molecular features that provide convenient handles for controlling the phosphorescence response have yet to be identified. We synthesized a series of phosphorescence zinc sensors based on a cyclometalated heteroleptic Ir(III) complex. The sensor construct includes two anionic cyclo-metalating ligands and a neutral diimine ligand that tethers a di(2-picolyl)amine (DPA) zinc receptor. A series of cyclo-metalating ligands with a range of electron densities and band gap energies were used to create phosphorescence sensors. The sensor series was characterized by variable-temperature steady-state and transient photoluminescence spectroscopy studies, electrochemical measurements, and quantum chemical calculations based on time-dependent density functional theory. The studies demonstrated that the suppression of nonradiative photoinduced electron transfer (PeT) from DPA to the photoexcited Ir-IV species provided the underlying mechanism that governed the phosphorescent response to zinc ions. Importantly, the Coulombic barrier, which was located on either the cyclometalating ligand or the diimine ligand, negligibly influenced the PeT process. Phosphorescence modulation by PeT strictly obeyed the Rehm-Weller principle, and the process occurred in the Marcus-normal region. These findings provide important guidelines for improving sensing performance; an efficient phosphorescence sensor should include a cyclometalating ligand with a wide band gap energy and a deep oxidation potential. Finally, the actions of the sensor were demonstrated by visualizing the intracellular zinc ion distribution in HeLa cells using a confocal laser scanning microscope and a photoluminescence lifetime imaging microscope.

  DOI：

  10.1021/ja3123202
• 作为产物：
  描述：

  4-甲基-1,10-邻二氮杂菲 在 selenium(IV) oxide 、 溶剂黄146 作用下， 以 1,4-二氧六环 、 甲醇 、 水 为溶剂， 反应 24.5h， 生成 4-(di(2-picolyl)aminomethyl)-1,10-phenanthroline
  参考文献：
  名称：

  Synthetic Control Over Photoinduced Electron Transfer in Phosphorescence Zinc Sensors

  摘要：

  Despite the promising photofunctionalities, phosphorescent probes have been examined only to a limited extent, and the molecular features that provide convenient handles for controlling the phosphorescence response have yet to be identified. We synthesized a series of phosphorescence zinc sensors based on a cyclometalated heteroleptic Ir(III) complex. The sensor construct includes two anionic cyclo-metalating ligands and a neutral diimine ligand that tethers a di(2-picolyl)amine (DPA) zinc receptor. A series of cyclo-metalating ligands with a range of electron densities and band gap energies were used to create phosphorescence sensors. The sensor series was characterized by variable-temperature steady-state and transient photoluminescence spectroscopy studies, electrochemical measurements, and quantum chemical calculations based on time-dependent density functional theory. The studies demonstrated that the suppression of nonradiative photoinduced electron transfer (PeT) from DPA to the photoexcited Ir-IV species provided the underlying mechanism that governed the phosphorescent response to zinc ions. Importantly, the Coulombic barrier, which was located on either the cyclometalating ligand or the diimine ligand, negligibly influenced the PeT process. Phosphorescence modulation by PeT strictly obeyed the Rehm-Weller principle, and the process occurred in the Marcus-normal region. These findings provide important guidelines for improving sensing performance; an efficient phosphorescence sensor should include a cyclometalating ligand with a wide band gap energy and a deep oxidation potential. Finally, the actions of the sensor were demonstrated by visualizing the intracellular zinc ion distribution in HeLa cells using a confocal laser scanning microscope and a photoluminescence lifetime imaging microscope.

  DOI：

  10.1021/ja3123202

文献信息

• Phosphorescent Sensor for Biological Mobile Zinc
  作者：Youngmin You、Sumin Lee、Taehee Kim、Kei Ohkubo、Weon-Sik Chae、Shunichi Fukuzumi、Gil-Ja Jhon、Wonwoo Nam、Stephen J. Lippard

  DOI：10.1021/ja207163r

  日期：2011.11.16

  zinc ions in a reversible and selective manner in buffered solution (pH 7.0, 25 mM PIPES) with K(d) = 11 nM and pK(a) = 4.16. Enhanced signal-to-noise ratios were achieved by time-gated acquisition of long-lived phosphorescence signals. The sensor was applied to image biological free zinc ions in live A549 cells by confocal laser scanning microscopy. A fluorescence lifetime imaging microscope detected

  基于带有两个 2-(2,4-二氟苯基)吡啶 (dfppy) 环金属化配体和中性 1,10-菲咯啉 (phen) 配体的 Ir(III) 配合物构建了一种新的磷光锌传感器 (ZIrF)。通过亚甲基接头在 phen 配体的 4 位引入了锌特异性二 (2-甲基吡啶) 胺 (DPA) 受体。阳离子 Ir(III) 复合物在 CH(3)CN 溶液中表现出双磷光带，分别源自 dfppy 和 phen 配体的蓝色和黄色发射。锌配位选择性地增强了后者，提供了磷光比率响应。电化学技术、量子化学计算以及稳态和飞秒光谱被用来建立这种磷光响应的光物理机制。研究表明，锌配位扰乱了 DPA 和 phen 之间发生的光诱导电子转移和配体内电荷转移跃迁的非发射过程。ZIrF 可以在 K(d) = 11 nM 和 pK(a) = 4.16 的缓冲溶液（pH 7.0，25 mM PIPES）中以可逆和选择性的方式检测锌离子。