N,N-diphenyl-4-(5-(6-phenyl-2,2'-bipyridin-4-yl)thiophen-2-yl)aniline | 1301629-54-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: N,N-diphenyl-4-(5-(6-phenyl-2,2'-bipyridin-4-yl)thiophen-2-yl)aniline
• 英文别名: N,N-diphenyl-4-[5-(2-phenyl-6-pyridin-2-ylpyridin-4-yl)thiophen-2-yl]aniline
• CAS: 1301629-54-8
• 化学式: C₃₈H₂₇N₃S
• 分子量: 557.718
• InChiKey: OEFNNXYLNWMQBH-UHFFFAOYSA-N

物化性质

• 沸点：
  701.7±60.0 °C(predicted)
• 密度：
  1.218±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  42
• 可旋转键数：
  7
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  57.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trichloro(trimethyl-4,4',4''-tricarboxylate-2,2':6',2''-terpyridine)ruthenium 、 N,N-diphenyl-4-(5-(6-phenyl-2,2'-bipyridin-4-yl)thiophen-2-yl)aniline 、 水 、 silver nitrate 在 N-ethylmorpholine 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 以71.1%的产率得到[Ru(N,N-diphenyl-4-(5-(6-phenyl-2,2'-bipyridin-4-yl)thiophen-2-yl)aniline(-1H))(trimethyl-4,4',4''-tricarboxylate-2,2':6',2''-terpyridine)]nitrate dihydrate
  参考文献：
  名称：

  用于光收集应用的功能化环金属化钌发色团的设计与开发

  摘要：

  报道了一组带有末端三苯胺（TPA）取代基的不对称双三齿环金属化Ru（II）配合物的合成和电化学光谱性质。这些配合物包含无机和有机染料共有的结构设计元素，在染料敏化太阳能电池（DSSC）中表现出优异的功率转换效率，这些配合物被广泛地配制为[Ru II（L-2,5'-thiophene-TPA） -R 1）（LR 2）] + [L =三齿螯合配体（例如2,2'：6'，2''-吡啶（tpy）； 1,3-二（吡啶-2-基）的去质子化形式）苯（Hdpb）或6-苯基-2,2'-联吡啶（Hpbpy））; R 1 = -H，-Me，-OMe; R 2 = -H，-CO2 Me，-CO 2 H]。以下结构属性进行了系统的修改，以便在系列：（ⅰ）供电子性的取代基终端（例如，R的字符1放置= -H，-Me，-OMe）对位为“L-2,5的胺'-噻吩-TPA-R 1 '配体框架；（ii）在TPA-取代的配体远端的三齿螯合物的吸电子特性（例如，R

  DOI：

  10.1021/ic200011m
• 作为产物：
  描述：

  1-(2-phenyl-2-oxoethyl)pyridinium iodide 在 四(三苯基膦)钯 、 ammonium acetate 、 potassium carbonate 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 28.0h， 生成 N,N-diphenyl-4-(5-(6-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

文献信息

• Design and Development of Functionalized Cyclometalated Ruthenium Chromophores for Light-Harvesting Applications
  作者：Kiyoshi C. D. Robson、Bryan D. Koivisto、Aswani Yella、Barbora Sporinova、Mohammad K. Nazeeruddin、Thomas Baumgartner、Michael Grätzel、Curtis P. Berlinguette

  DOI：10.1021/ic200011m

  日期：2011.6.20

  character of the tridentate chelate distal to the TPA-substituted ligand (e.g., R2 = −H, −CO2Me, −CO2H); and (iii) position of the organometallic bond about the Ru(II) center. UV–vis spectra reveal intense and broad absorption bands arising from a collection of metal-to-ligand charge-transfer (MLCT) and TPA-based intraligand charge-transfer (ILCT) transitions that, in certain cases, extend beyond 800

  报道了一组带有末端三苯胺（TPA）取代基的不对称双三齿环金属化Ru（II）配合物的合成和电化学光谱性质。这些配合物包含无机和有机染料共有的结构设计元素，在染料敏化太阳能电池（DSSC）中表现出优异的功率转换效率，这些配合物被广泛地配制为[Ru II（L-2,5'-thiophene-TPA） -R 1）（LR 2）] + [L =三齿螯合配体（例如2,2'：6'，2''-吡啶（tpy）； 1,3-二（吡啶-2-基）的去质子化形式）苯（Hdpb）或6-苯基-2,2'-联吡啶（Hpbpy））; R 1 = -H，-Me，-OMe; R 2 = -H，-CO2 Me，-CO 2 H]。以下结构属性进行了系统的修改，以便在系列：（ⅰ）供电子性的取代基终端（例如，R的字符1放置= -H，-Me，-OMe）对位为“L-2,5的胺'-噻吩-TPA-R 1 '配体框架；（ii）在TPA-取代的配体远端的三齿螯合物的吸电子特性（例如，R
• Systematic Modulation of a Bichromic Cyclometalated Ruthenium(II) Scaffold Bearing a Redox-Active Triphenylamine Constituent
  作者：Kiyoshi C. D. Robson、Barbora Sporinova、Bryan D. Koivisto、Eduardo Schott、Douglas G. Brown、Curtis P. Berlinguette

  DOI：10.1021/ic1025679

  日期：2011.7.4

  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.