[Re(4,4'-dicarboxyl-2,2'-bipyridine)(CO)3(CF3SO3)] | 1131873-88-5

• 英文名称: [Re(4,4'-dicarboxyl-2,2'-bipyridine)(CO)3(CF3SO3)]
• 英文别名: [Re(4,4'-(CO2H)2-bpy)(CO)3(CF3SO3)]
• CAS: 1131873-88-5
• 化学式: C₁₆H₈F₃N₂O₁₀ReS
• 分子量: 663.515
• InChiKey: MAVHUZNZWRCISB-UHFFFAOYSA-M

计算性质

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

反应信息

• 作为反应物：
  描述：

  [Re(4,4'-dicarboxyl-2,2'-bipyridine)(CO)3(CF3SO3)] 以 四氢呋喃 为溶剂， 生成 [Re(4,4'-dicarboxyl-2,2'-bipyridine)(CO)3(OH)]
  参考文献：
  名称：

  Improvement of the Dynamic Range of pH Sensing by Using a Luminescent Tricarbonylpolypyridylrhenium(I) Complex with Three Different Protonation Sites

  摘要：

  The complex [Re(4,4'-(CO2H)(2)-bpy)(CO)(3)(4,4'-bpy)](CF3SO3), 1 (4,4'-(CO2H)(2)-bpy = 4,4'-dicarboxyl-2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine), synthesized and characterized by spectroscopic techniques, displays a strong dependence of its photophysical properties on pH. From both emission intensity and lifetime measurements at different pH values, three values for the protonation constants of the excited states have been determined (pK(a1)* = 1.8 +/- 0.1, pK(a2)* = 3.9 +/- 0.1, and pK(a3)* = 5.6 +/- 0.1). The unusual bell-shaped variations of these photophysical properties can be accounted for by the changes of energy level orderings induced by each protonation, as confirmed by time-dependent density functional theory (TD-DFT) calculations. Since the solubility, stability, and dynamic range of pH sensing by 1 have been improved with respect to similar tricarbonylpolypyridylrhenium(I) complexes, we conclude that 1 can be used as an efficient molecular switch of the on-off-on type.

  DOI：

  10.1021/ic802203d
• 作为产物：
  描述：

  2,2'-联吡啶-4,4'-二甲酸 以 四氢呋喃 、 甲苯 为溶剂， 生成 [Re(4,4'-dicarboxyl-2,2'-bipyridine)(CO)3(CF3SO3)]
  参考文献：
  名称：

  Improvement of the Dynamic Range of pH Sensing by Using a Luminescent Tricarbonylpolypyridylrhenium(I) Complex with Three Different Protonation Sites

  摘要：

  The complex [Re(4,4'-(CO2H)(2)-bpy)(CO)(3)(4,4'-bpy)](CF3SO3), 1 (4,4'-(CO2H)(2)-bpy = 4,4'-dicarboxyl-2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine), synthesized and characterized by spectroscopic techniques, displays a strong dependence of its photophysical properties on pH. From both emission intensity and lifetime measurements at different pH values, three values for the protonation constants of the excited states have been determined (pK(a1)* = 1.8 +/- 0.1, pK(a2)* = 3.9 +/- 0.1, and pK(a3)* = 5.6 +/- 0.1). The unusual bell-shaped variations of these photophysical properties can be accounted for by the changes of energy level orderings induced by each protonation, as confirmed by time-dependent density functional theory (TD-DFT) calculations. Since the solubility, stability, and dynamic range of pH sensing by 1 have been improved with respect to similar tricarbonylpolypyridylrhenium(I) complexes, we conclude that 1 can be used as an efficient molecular switch of the on-off-on type.

  DOI：

  10.1021/ic802203d

文献信息

• Synthesis and characterization of rhenium(I) 4,4′-dicarboxy-2,2′-bipyridine tricarbonyl complexes for solar energy conversion
  作者：Venugopal Komreddy、Kevin Ensz、Huy Nguyen、D. Paul Rillema

  DOI：10.1016/j.ica.2020.119815

  日期：2020.10

  Abstract The synthesis of a series of rhenium(I) tricarbonyl complexes containing 4,4′-dicarboxy-2,2′-bipyridine (dcbpy) and various halide or pseudohalide ligands is reported. Deprotonation of the carboxylates occurs in basic medium resulting in upfield 1H NMR shifts for the protons of the carboxyl groups attached to 2,2′-bipyridine. Metal-to-ligand charge transfer (MLCT) due to dπ → π* transitions

  摘要报道了一系列含4,4'-二羧基-2,2'-联吡啶（dcbpy）和各种卤化物或拟卤化物配体的tri（I）三羰基配合物的合成。羧酸盐的去质子化在碱性介质中发生，导致连接到2,2'-联吡啶的羧基质子的高场1H NMR位移。由于dπ→π*跃迁导致的金属到配体的电荷转移（MLCT）在卤化物序列中从Re（dcbpy）（CO）3F的382 nm系统地转移到Re（dcbpy）（CO）3I的436 nm。这些化合物在600–650 nm范围内发射，并且发射寿命大于50 ns。在Gratzel电池中使用TiO2-Re（dcbpy）（CO）3X（X = F，CN，SCN，Br，I）和光阳极时，太阳能转换效率不到1％。