4'-(5-bromo-thiophen-2-yl)-[2,2';6',2'']terpyridine | 496859-94-0

• 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-bromo-thiophen-2-yl)-[2,2';6',2'']terpyridine
• 英文别名: 4'-(5-bromo-2-thienyl)-2,2':6',2''-terpyridine；4’-(5-bromothien-2-yl)-2,2’:6’,2’’-terpyridine；4′-(5-bromo-2-thienyl)-2,2′:6′,2″-terpyridine；4′-(5-bromothiophene-2-yl)-2,2′:6′2″-terpyridine；4'-(2-bromo-5-thienyl)-2,2':6',2''-terpyridine；4'-(5-bromothiophene)-2,2',6',2''-terpyridine；2,2':6',2''-Terpyridine, 4'-(5-bromo-2-thienyl)-；4-(5-bromothiophen-2-yl)-2,6-dipyridin-2-ylpyridine
• CAS: 496859-94-0
• 化学式: C₁₉H₁₂BrN₃S
• 分子量: 394.294
• InChiKey: PLOITYRMGFAVRB-UHFFFAOYSA-N

物化性质

• 熔点：
  215 °C
• 沸点：
  497.5±40.0 °C(Predicted)
• 密度：
  1.456±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  66.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4'-(5-bromo-thiophen-2-yl)-[2,2';6',2'']terpyridine 在 sodium azide 、 氯化铵 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 59.33h， 生成 TPDTZPB
  参考文献：
  名称：

  COMPOUNDS USEFUL AS LIGANDS AND PARTICULARLY AS ORGANIC CHROMOPHORES FOR COMPLEXING LANTHANIDES AND APPLICATIONS THEREOF

  摘要：

  本发明涉及使用包含至少一个2-(1H-四唑-5-基)吡啶单元的化合物，其化学式如下所示，作为镧系元素的配体，更特别地，作为这些元素的有机荧光团。同时，还涉及使用这些化合物作为有机荧光团形成镧系元素配合物，以及含有一个或多个2-(1H-四唑-5-基)吡啶单元的新化合物，这些化合物可作为镧系元素的配体，尤其是作为这些元素的有机荧光团。应用领域包括光子学和光电子学，特别是用于制造发光器件如电致发光二极管；生物学，例如用于制备发光探针。

  公开号：

  US20110112289A1
• 作为产物：
  描述：

  4'-(2-thienyl)-2,2':6',2''-terpyridine 在 N-溴代丁二酰亚胺(NBS) 作用下， 生成 4'-(5-bromo-thiophen-2-yl)-[2,2';6',2'']terpyridine
  参考文献：
  名称：

  Synthesis and photophysical properties of α,ω-bis(terpyridine)oligothiophenes

  摘要：

  Four novel fully pi-conjugated alpha,omega-bis(terpyridine)oligothiophenes characterized by NMR, IR, and HR-mass spectroscopy are presented and their electronic absorption/emission and redox properties are described based on both experiments and theoretical calculations. These compounds can be potentially utilized as building blocks for preparation of conjugated metallo-supramolecular polymers or dynamers and related functional materials. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.11.039

文献信息

• Preparation and photophysical properties of precursors of inorganic macromolecules. Mono and binuclear complexes of Ru(II) and terpyridine derivatized with thiophene and 4′-(5-bromothiophene) groups
  作者：R. López、D. Villagra、G. Ferraudi、S.A. Moya、J. Guerrero

  DOI：10.1016/j.ica.2004.02.038

  日期：2004.9

  The preparation and characterization of mono and binuclear complexes of Ru(II) with a newly synthesized derivate of the terpyridine ligand, 4′-(5-bromothiophene)-2,2′,6′,2″-terpyridine, are communicated. In the binuclear complex, 2,5-bis(2,2′,6′,2″-terpyridine-4′yl)thiophene was used as a bridge between two Ru(II) centers. The new compounds were characterized by H NMR, UV–Vis and IR spectroscopies

  介绍了Ru（II）与新合成的叔吡啶配体4'-（5-溴噻吩）-2,2'，6'，2''-叔吡啶的衍生物的单核和双核配合物的制备和表征。在双核络合物中，将2,5-双（2,2'，6'，2''-叔吡啶-4'基）噻吩用作两个Ru（II）中心之间的桥。新化合物通过1 H NMR，UV-Vis和IR光谱进行表征。在络合物的UV-Vis光谱中观察到Ru（II）到吡啶的电荷转移跃迁在〜500 nm处的谱带，以及在λ<400 nm处分配给配体内跃迁的吸收谱带π*←π，居中于tpy部分。在337或500 nm的CH3CN中辐照配合物可诱导发光，最大发光波长约为670 nm，寿命为τ⩽102ns。时间分辨吸收光谱揭示了在金属向配体电荷转移的激发态衰变过程中长寿命物种的形成。中间体暂定为配体取代或正金属化激发态反应的不稳定产物。
• Alcohol- and water-soluble bis(tpy)quaterthiophenes with phosphonium side groups: new conjugated units for metallo-supramolecular polymers
  作者：P. Štenclová、K. Šichová、I. Šloufová、J. Zedník、J. Vohlídal、J. Svoboda

  DOI：10.1039/c5dt04133c

  日期：——

  Bis(tpy)quaterthiophenes with symmetrically distributed two and four 6-bromohexyl side groups were prepared and modified by the reaction with triethylphosphine to give the corresponding ionic species.

  对称分布有两个和四个6-溴己基侧链的双(三吡啶基)四噻吩经过与三乙基膦反应进行改性，得到相应的离子物种。
• Remarkable Tuning of the Coordination and Photophysical Properties of Lanthanide Ions in a Series of Tetrazole-Based Complexes
  作者：Eugen S. Andreiadis、Renaud Demadrille、Daniel Imbert、Jacques Pécaut、Marinella Mazzanti

  DOI：10.1002/chem.200900912

  日期：2009.9.21

  bipyridine‐based (25 nm) complexes towards the visible region (up to 440 nm). Moreover, the substitution of the terpyridine–tetrazolate system with different groups in the ligand series L3–L6 has a very important effect on both absorption spectra and luminescence efficiency of their lanthanide complexes. The tetrazole‐based ligands L1 and L3–L8 sensitize efficiently the luminescent emission of lanthanide ions in the

  合成了一系列七个新的基于四唑的配体（L1，L3-L8），它们含有适合形成镧系元素发光络合物的联吡啶或联吡啶发色团。通过叠氮化钠的热环加成，由各自的腈制备所有配体。均三联吡啶-四唑酸盐配合物[Ln（L i）2 ] NHEt 3（对于i = 1，2为Ln = Nd，Eu，Tb ；对于i = 3，4为Ln = Eu ）和一水合吡啶的晶体结构–四唑酸盐配合物[Eu（H 2 O）（L7）2 ] NHEt 3被确定。四齿联吡啶-四唑酸盐配体形成非螺旋络合物，其中可能包含与金属配位的水分子。相反，五齿的叔吡啶-四唑酸盐配体包裹金属，从而防止溶剂配位并形成类似手性吡啶-羧酸盐的手性双螺旋络合物。质子NMR光谱研究表明，这些络合物的固态结构保留在溶液中，并表明了三联吡啶-四唑酸盐疏水络合物的动力学稳定性。紫外光谱结果表明，联吡啶-四唑酸盐配合物的稳定性与其羧酸酯类似物相似，这足以在有氧条件下将其分离出来。用
• Synthesis and applications of main-chain Ru(<scp>ii</scp>) metallo-polymers containing bis-terpyridyl ligands with various benzodiazole cores for solar cells
  作者：Harihara Padhy、Duryodhan Sahu、I-Hung Chiang、Dhananjaya Patra、Dhananjay Kekuda、Chih-Wei Chu、Hong-Cheu Lin

  DOI：10.1039/c0jm02532a

  日期：——

  A series of π-conjugated bis-terpyridyl ligands (M1–M3) bearing various benzodiazole cores and their corresponding main-chain Ru(II) metallo-polymers were designed and synthesized. The formation of metallo-polymers were confirmed by NMR, relative viscosity, and UV-visible titration measurements. The effects of electron donor and acceptor interactions on their thermal, optical, electrochemical, and photovoltaic properties were investigated. Due to the strong intramolecular charge transfer (ICT) interaction and metal to ligand charge transfer (MLCT) in Ru(II)-containing polymers, the absorption spectra covered a broad range of 260–750 nm with the optical band gaps of 1.77–1.63 eV. In addition, due to the broad sensitization areas of the metallo-polymers, their bulk heterojunction (BHJ) solar cell devices containing [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as an electron acceptor exhibited a high short-circuit current (Jsc). An optimum PVC device based on the blended polymer P1 : PCBM = 1 : 1 (w/w) achieved the maximum power conversion efficiency (PCE) value up to 0.45%, with Voc = 0.61 V, Jsc = 2.18 mA cm−2, and FF = 34.1% (under AM 1.5 G 100 mW cm−2), which demonstrated a novel family of conjugated polyelectrolytes with the highest PCE value comparable with BHJ solar cells fabricated from ionic polythiophene and C60.

  我们设计并合成了一系列含有各种苯并二唑核心的 π 共轭双叔吡啶配体（M1-M3）及其相应的主链 Ru(II) 金属聚合物。核磁共振、相对粘度和紫外-可见滴定测量证实了金属聚合物的形成。研究了电子供体和受体相互作用对其热学、光学、电化学和光伏特性的影响。由于含 Ru(II)聚合物具有很强的分子内电荷转移（ICT）作用和金属到配体的电荷转移（MLCT）作用，其吸收光谱覆盖了 260-750 nm 的宽范围，光带隙为 1.77-1.63 eV。此外，由于金属聚合物的敏化区域较宽，其含有[6,6]-苯基-C61-丁酸甲酯（PCBM）作为电子受体的体异质结（BHJ）太阳能电池器件显示出较高的短路电流（Jsc）。基于混合聚合物 P1 ：PCBM = 1 ：1（w/w）的聚氯乙烯器件实现了最高功率转换效率（PCE）值达 0.45%，Voc = 0.61 V，Jsc = 2.18 mA cm-2，FF = 34.1%（在 AM 1.5 G 100 mW cm-2 条件下），这表明一种新型共轭聚电解质系列具有与离子聚噻吩和 C60 制成的 BHJ 太阳能电池相当的最高 PCE 值。
• Zinc(II) and Ruthenium(II) Complexes of Novel Fluorene Substituted Terpyridine Ligands: Synthesis, Spectroscopy and Electrochemistry
  作者：K. R. Justin Thomas、J. T. Lin、Chen-Pin Chang、Chang-Hao Chuen、Chung-Chin Cheng

  DOI：10.1002/jccs.200200119

  日期：2002.10

  Terpyridine ligands substituted with fluorene, fluorenylethynylthiophene and fluorenylethynylbenzene were obtained by applying Krohnke synthesis and Sonogashira coupling reactions. [ZnL 2 ] 2 + and [Ru(L)-(tpy)] 2 + complexes were obtained by standard methods and characterized by spectroscopic and electrochemical methods. Zinc complexes are bright luminophores emitting blue to yellow colors depending

  采用Krohnke合成和Sonogashira偶联反应得到芴、芴基乙炔基噻吩和芴基乙炔基苯取代的三联吡啶配体。[ZnL 2 ] 2 + 和[Ru(L)-(tpy)] 2 + 配合物通过标准方法获得，并通过光谱和电化学方法进行表征。锌配合物是明亮的发光体，根据配体中的共轭性质发出蓝色至黄色，而钌配合物在室温下不发光。高量子产率和短寿命表明锌配合物中的发射主要以配体为中心。