4-(5-bromothiophen-2-yl)-6-(3-(trifluoromethyl)phenyl)-2,2'-bipyridine | 1310370-99-0

• 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: 4-(5-bromothiophen-2-yl)-6-(3-(trifluoromethyl)phenyl)-2,2'-bipyridine
• 英文别名: 4-(5-bromothiophen-2-yl)-6-[3-(trifluoromethyl)phenyl]-2,2'-bipyridine
• CAS: 1310370-99-0
• 化学式: C₂₁H₁₂BrF₃N₂S
• 分子量: 461.305
• InChiKey: XIIOJPRSBRUYNN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.32
• 重原子数：
  28.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  25.78
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-(二苯基氨基)苯硼酸频那醇酯 、 4-(5-bromothiophen-2-yl)-6-(3-(trifluoromethyl)phenyl)-2,2'-bipyridine 在 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 14.0h， 以81.6%的产率得到N,N-diphenyl-4-[5-[6-[3-(trifluoromethyl)phenyl]-2,2'-bipyridin-4-yl]thiophen-2-yl]aniline
  参考文献：
  名称：

  Systematic Modulation of a Bichromic Cyclometalated Ruthenium(II) Scaffold Bearing a Redox-Active Triphenylamine Constituent

  摘要：

  The syntheses and physicochemical properties of nine bis-tridentate ruthenium(II) complexes containing one cyclometalating ligand furnished with terminal triphenylamine (TPA) substituents are reported. The structure of each complex conforms to a molecular scaffold formulated as [Ru-II(TPA-2,5-thiophene-pbpy)(Me(3)tctpy)] (pbpy = 6-phenyl-2,2'-bipyridine; Me(3)tctpy = trimethyl-4,4',4 ''-tricarboxylate-2,2':6',2 ''-terpyridine), where various electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) are installed about the TPA unit and the anionic ring of the pbpy ligand. It is found that the redox chemistry of the Ru center and the TPA unit can be independently modulated by (i) placing EWGs (e.g., -CF3) or EDGs (e.g., -OMe) on the anionic ring of the pbpy ligand (substituted sites denoted as R-2 or R-3) and/or (ii) installing electron-donating substituents (e.g., -H, -Me, -OMe) para to the amine of the TPA group (i.e., R-1). The first oxidation potential is localized to the TPA unit when, for example, EDGs are placed at R-1 with EWGs at R-2 (e.g., the TPA(center dot+)/TPA(0) and Ru-III/Ru-II redox couples appear at +0.98 and +1.27 V vs NHE, respectively, when R-1 = -OMe and R-2 = -CF3). This situation is reversed when R-3 = EDG and R-1 = -H: TPA-based and metal-centered oxidation waves occur at +1.20 and +1.11 V vs NHE, respectively. The UV-vis spectrum for each complex is broad (e.g., absorption bands are extended from the UV region to beyond 800 nm in all cases) and intense (e.g., epsilon similar to 10(4) M-1 . cm(-1)) because of the overlapping intraligand charge-transfer and metal-to-ligand charge-transfer transitions. The information derived from this study offers guiding principles for modulating the physicochemical properties of bichromic cyclometalated ruthenium(II) complexes.

  DOI：

  10.1021/ic1025679
• 作为产物：
  描述：

  1-[2-oxo-2-[3-(trifluoromethyl)phenyl]ethyl]pyridinium iodide 、 (E)-3-(5-bromothiophen-2-yl)-1-(pyridin-2-yl)prop-2-en-1-one 在 ammonium acetate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 14.0h， 以73.3%的产率得到4-(5-bromothiophen-2-yl)-6-(3-(trifluoromethyl)phenyl)-2,2'-bipyridine
  参考文献：
  名称：

  Systematic Modulation of a Bichromic Cyclometalated Ruthenium(II) Scaffold Bearing a Redox-Active Triphenylamine Constituent

  摘要：

  The syntheses and physicochemical properties of nine bis-tridentate ruthenium(II) complexes containing one cyclometalating ligand furnished with terminal triphenylamine (TPA) substituents are reported. The structure of each complex conforms to a molecular scaffold formulated as [Ru-II(TPA-2,5-thiophene-pbpy)(Me(3)tctpy)] (pbpy = 6-phenyl-2,2'-bipyridine; Me(3)tctpy = trimethyl-4,4',4 ''-tricarboxylate-2,2':6',2 ''-terpyridine), where various electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) are installed about the TPA unit and the anionic ring of the pbpy ligand. It is found that the redox chemistry of the Ru center and the TPA unit can be independently modulated by (i) placing EWGs (e.g., -CF3) or EDGs (e.g., -OMe) on the anionic ring of the pbpy ligand (substituted sites denoted as R-2 or R-3) and/or (ii) installing electron-donating substituents (e.g., -H, -Me, -OMe) para to the amine of the TPA group (i.e., R-1). The first oxidation potential is localized to the TPA unit when, for example, EDGs are placed at R-1 with EWGs at R-2 (e.g., the TPA(center dot+)/TPA(0) and Ru-III/Ru-II redox couples appear at +0.98 and +1.27 V vs NHE, respectively, when R-1 = -OMe and R-2 = -CF3). This situation is reversed when R-3 = EDG and R-1 = -H: TPA-based and metal-centered oxidation waves occur at +1.20 and +1.11 V vs NHE, respectively. The UV-vis spectrum for each complex is broad (e.g., absorption bands are extended from the UV region to beyond 800 nm in all cases) and intense (e.g., epsilon similar to 10(4) M-1 . cm(-1)) because of the overlapping intraligand charge-transfer and metal-to-ligand charge-transfer transitions. The information derived from this study offers guiding principles for modulating the physicochemical properties of bichromic cyclometalated ruthenium(II) complexes.

  DOI：

  10.1021/ic1025679

文献信息

• Novel triphenylamine-modified ruthenium(ii) terpyridine complexes for nickel oxide-based cathodic dye-sensitized solar cells
  作者：Christopher J. Wood、Kiyoshi C. D. Robson、Paul I. P. Elliott、Curtis P. Berlinguette、Elizabeth A. Gibson

  DOI：10.1039/c3ra44690e

  日期：——

  A pair of ruthenium based donor-π-chromophore sensitizers (K1 and K2) have been synthesized for use in NiO based p-type dye sensitized solar cells (p-DSCs). The optical and electrochemical properties of these dyes were determined experimentally and interpreted by DFT modelling. NiO p-DSC devices incorporating these dyes gave photocurrents of 2.9 for K1 and 2.0 mA cm−2 for K2 (IPCE of 14% and 9%); this is a vast improvement on the photocurrents of p-DSC devices incorporating ‘traditional’ ruthenium sensitizers.

  我们合成了一对基于钌的供体-π-色素敏化剂（K1 和 K2），用于基于氧化镍的对型染料敏化太阳能电池（p-DSCs）。实验测定了这些染料的光学和电化学特性，并通过 DFT 建模对其进行了解释。含有这些染料的氧化镍对型染料敏化太阳能电池装置的 K1 光电流为 2.9 mA cm-2，K2 为 2.0 mA cm-2（IPCE 分别为 14% 和 9%）；与含有 "传统 "钌敏化剂的对型染料敏化太阳能电池装置的光电流相比，这是一个巨大的进步。