(2,2':6',2''-terpyridine-C2-(ferrocene)2-C2-2,2':6',2''-terpyridine) | 886525-44-6

• 英文名称: (2,2':6',2''-terpyridine-C2-(ferrocene)2-C2-2,2':6',2''-terpyridine)
• 英文别名: tpy-C2-(fc)2-C2-tpy；1,1'-bis(terpyridylethynyl)biferrocene；1,1'-bis(2,2':6',2''-terpyridin-4'-yl-ethynyl)diferrocene
• CAS: 886525-44-6
• 化学式: C₅₄H₃₆Fe₂N₆
• 分子量: 880.614
• InChiKey: FBMKBWILAOMBSJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  ammonium hexafluorophosphate 、 Ru(4'-chloro-2,2':6',2''-terpyridine)Cl3 、 (2,2':6',2''-terpyridine-C2-(ferrocene)2-C2-2,2':6',2''-terpyridine) 在 N-ethylmorpholine 作用下， 以 乙醇 、 水 为溶剂， 以50%的产率得到(4'-Cl-tpy)Ru(II)(tpy-C2-(fc)2-C2-tpy)Ru(II)(4'-Cl-tpy)(PF6)4
  参考文献：
  名称：

  跨双核钌（II）联吡啶络合物中的氧化还原活性二茂铁间隔基的电子耦合微调制：合成，电化学和光物理性质。

  摘要：

  [[X- tpy ）Ru II（tpy-（fc）2 -tpy）Ru II（X- tpy ）] 4+的电化学和光物理性质（tpy =吡啶基; X = -H（1a），-OCH 3（1b），-Cl（1c）; fc =二茂铁基）和[[X-tpy）Ru II（tpy-C≡C-（fc）2 -C≡C-tpy）Ru II（X-tpy）] 4 +（X = -H（2a），-OCH 3（2b），-Cl（2c））进行了说明。通过电化学测量探测基态HOMO和LUMO能量。紫外可见吸收光谱和发光光谱探测了激发态的光物理性质。的复合物1A - Ç是非发射（λ EXC在脱氧的纯CH 480-580纳米）3 CN或H 2 O / CH 3 CN（4/1）溶液在25℃下。络合物2a - c在H 2 O / CH 3 CN（4/1）溶液中具有室温发光。比较2b，c和2a的发光特性，-OCH 3和-Cl取代基的附着导致发光量子产率的降低和三重态寿命的降低。

  DOI：

  10.1021/om700568h
• 作为产物：
  描述：

  1',1'''-bis(ethynyl)biferrocene 、 4'-{[(Trifluoromethyl)sulfonyl]oxy}-2,2':6',2''-terpyridine 在 四(三苯基膦)钯 diisopropylamine 作用下， 以 四氢呋喃 为溶剂， 以30%的产率得到(2,2':6',2''-terpyridine-C2-(ferrocene)2-C2-2,2':6',2''-terpyridine)
  参考文献：
  名称：

  Toward the Development of Molecular Wires:  A Terpyridine Spacer Containing Polyferrocenylalkyne Linkages

  摘要：

  The preparation, characterizations, and electrochemical measurements of the terpyridine-ferrocenylalkyne spacers (tpy-C C-(fc)(n)-C C-tpy; tpy = terpyridyl; fc = ferrocenyl; n = 2, 3) are described. In the electrochemical measurements, the charge could be delocalized to the cyclopentadienyl and ethynyl moieties caused by the built-up charge density upon oxidation of the ferrocenyl moiety.

  DOI：

  10.1021/om051061e

文献信息

• Synthesis, electrochemistry, and photophysical properties of binuclear ruthenium(II)–terpyridine complexes comprising redox-active ferrocenyl spacer
  作者：Teng-Yuan Dong、Mei-Ching Lin、Shu-Wei Chang、Chih-Chien Ho、Shu-Fan Lin、Liangshiu Lee

  DOI：10.1016/j.jorganchem.2007.02.007

  日期：2007.5

  In attempting to perturb the electronic properties of the spacer, we now describe an interesting example of Ru2+-tpy (tpy = terpyridine) complexes with 1,1'-bis(ethynyl)polyferrocenyl moiety attached directly to the 4'-position of the tpy ligand (tpy-C=C-(fc)(n)-C=C-tpy; fc = ferrocenyl; n = 2-3). Complexes of Ru2+-tpy have room-temperature luminescence in H2O/CH3CN (4/1) solution. The ground-state HOMO and LUMO energies were probed by electrochemical measurements and the excited-state photophysical properties were probed by UV-Vis absorption spectroscopy and luminescence spectroscopy. The redox behavior of [(tpy)Ru-II-tpy-C=C-(fc)(n)-C=C tpy-Ru-II(tpy)](4+) complex is dominated by the Ru2+/Ru3+ redox couple (E-1/2 from 135 to 1.39 V), Fe2+/Fe3+ redox couples (E-1/2 from 0.4 to 1.0 V) and tpy/tpy(-)/tpy(2-) redox couples (E-1/2 from -1.3 to -1.5 V). Electrochemical data, UV absorption and emission spectra indicate that the pi-delocalization in the spacer is enhanced by the insertion of ethynyl unit. Interestingly, the insertion of ethynyl unit into the main chain causes a dramatic increase of phosphorescence yield (1.48 x 10(-4) for n = 2; 1.13 x 10(-4) for n = 3), triplet lifetime (67 ns for n = 2; 24 ns for n = 3), and emission intensity. The biferrocenyl spacer can be converted into mixed-valence biferrocenium spacer, which gives a more effective pi-delocalization along main chain, by selective chemical oxidation of ferrocenyl unit. In deoxygenated H2O/CH3CN (4/1) solution at 25 degrees C, the oxidized complex of [(tpy)Ru-II-tpy-C=C-(fc)(2)-C=C-tpy-Ru-II(tpy)](5+) is nonemissive. The presence of lower energy ferroceanium-centered [Ru-a(II)-tpy(-)-fc(III)-fc(III)-tpy-Ru-b(II)] excited-state provides an additional channel for excited-state decay. The mixed-valence biferrocenium center acts as an efficient quencher for the MLCT excited-state. (C) 2007 Elsevier B.V. All rights reserved.