6,6''-Diphenyl-2,2':6',2''-terpyridine | 85575-96-8

• 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: 6,6''-Diphenyl-2,2':6',2''-terpyridine
• 英文别名: 6,6''-diphenyl 2,2',6',2''-terpyridine；2,6-bis(6-phenylpyridin-2-yl)pyridine
• CAS: 85575-96-8
• 化学式: C₂₇H₁₉N₃
• 分子量: 385.468
• InChiKey: USFZOZZHZXUYGC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6,6''-Diphenyl-2,2':6',2''-terpyridine 、 iron(II) bromide 以 not given 为溶剂， 以86%的产率得到
  参考文献：
  名称：

  Catalytic Hydrosilylation of Alkenes by Iron Complexes Containing Terpyridine Derivatives as Ancillary Ligands

  摘要：

  Iron complexes formulated as Fe(terpy)X-2 (terpy = 2,2':6',2 ''-terpyridine derivatives; X = Cl, Br) were prepared and their catalytic activities for hydrosilylation of olefin with hydrosilane were examined. Although Fe(terpy)X-2 did not show catalytic activity, the treatment of Fe(terpy)X-2 with NaHBEt3 caused catalytic activity. The influence of substituents in terpy on the catalytic activity was examined, and it was found that some complexes with an unsymmetrically disubstituted terpy selectively produced 1-silylalkane with quite high catalytic activity. In the reaction of 1-octene with PhSiH3, the double-hydrosilylation product Ph(1-octyl)(2)SiH was selectively obtained.

  DOI：

  10.1021/om300279t
• 作为产物：
  描述：

  6,6′′-二溴-2,2′:6′,2′′-三联吡啶 、 苯硼酸 在 四(三苯基膦)钯 、 sodium carbonate 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 12.0h， 以95%的产率得到6,6''-Diphenyl-2,2':6',2''-terpyridine
  参考文献：
  名称：

  Iron-Catalyzed Hydrogen Production from Formic Acid

  摘要：

  Hydrogen represents a clean energy source, which can be efficiently used in fuel cells generating electricity with water as the only byproduct. However, hydrogen generation from renewables under mild conditions and efficient hydrogen storage in a safe and reversible manner constitute important challenges In this respect formic acid (HCO2H) represents a convenient hydrogen storage material, because it is one of the major products from biomass and can undergo selective decomposition to hydrogen and carbon dioxide in the presence of suitable catalysts. Here, the first light-driven iron-based catalytic system for hydrogen generation from formic acid is reported By application of a catalyst formed in situ from inexpensive Fe-3(CO)(12), 2,2'.6'2"-terpyridine or 1,10-phenanthroline, and triphenylphosphine, hydrogen generation is possible under visible light irradiation and ambient temperature. Depending on the kind of N-ligands significant catalyst turnover numbers (>100) and turnover frequencies (up to 200 h(-1)) are observed, which are the highest known to date for nonprecious metal catalyzed hydrogen generation from formic acid NMR, IR studies, and DFT calculations of iron complexes, which are formed under reaction conditions, confirm that PPh3 plays an active role in the catalytic cycle and that N-ligands enhance the stability of the system It is shown that the reaction mechanism includes iron hydride species which are generated exclusively under irradiation with visible light

  DOI：

  10.1021/ja100925n

文献信息

• Phenyl-substituted 2,2′:6′,2″-terpyridine as a new series of fluorescent compounds—their photophysical properties and fluorescence tuning
  作者：Toshiki Mutai、Jin-Dong Cheon、Shinpei Arita、Koji Araki

  DOI：10.1039/b102685m

  日期：——

  Several phenyl-substituted 2,2′:6′,2″-terpyridines (tpy) were synthesized and it was found that 4′-phenyl tpy (ptp, 3) exhibited the most effective fluorescence, whose quantum yield was up to 0.64 in cyclohexane. For further study on tuning the fluorescence properties of ptp, different substituents were introduced into the p-position of the phenyl group. While Br- 10, Cl- 11, and CH3-ptp 12 showed their absorption and fluorescence in the same region as 3, those of NH2- 14 and Me2N-ptp 15 were observed at much longer wavelengths. In addition, fluorescence maxima of 14 and 15 showed large (>130 nm) solvent dependence. The difference between ground and excited state dipole moment (Δμ) for 15 was estimated to be 15.2 D by the Lippert–Mataga equation, indicating the intramolecular charge transfer (ICT) process. Semi-empirical MO calculation (MOPAC/AM1) demonstrated that the HOMO-1, HOMO and LUMO of 3, 10–12 were mainly localized on the phenyl (πph), tpy (πtpy) and tpy (π*tpy) part, respectively, indicating that the lowest energy absorption band of 3, 10–12 was the local excitation (πtpy–π*tpy). In the case of 14 and 15, which have an electron-donating substituent, πph instead of πtpy became the HOMO. Thus, the lowest energy absorption of 14 and 15 was an ICT transition (πph–π*tpy), and a large red shift of the fluorescence occurred. In these compounds, the energy level of πph is controlled without affecting that of πtpy and π*tpy, suggesting a novel approach for tuning the color of fluorescence.

  合成了几种苯基取代的2,2':6',2''-三联吡啶（tpy），发现4'-苯基tpy（ptp，3）具有最有效的荧光，其在环己烷中的量子产率高达0.64。为了进一步研究调节ptp的荧光性质，将不同的取代基引入苯环的p位。Br-10，Cl-11和CH3-ptp 12显示与3相同的吸收和荧光区域，而NH2-14和Me2N-ptp 15的吸收和荧光则在更长的波长处被观察到。此外，14和15的荧光最大值显示了大于130 nm的溶剂依赖性。根据Lippert-Mataga方程，15的基态和激发态偶极矩差（Δμ）估计为15.2 D，表明存在分子内电荷转移（ICT）过程。半经验MO计算（MOPAC/AM1）表明，3、10-12的HOMO-1、HOMO和LUMO主要分别定域在苯基（πph）、tpy（πtpy）和tpy（π*tpy）部分，表明3、10-12的最低能量吸收带是局部激发（πtpy-π*tpy）。对于具有电子给体取代基的14和15，πph而非πtpy成为HOMO。因此，14和15的最低能量吸收是ICT跃迁（πph-π*tpy），并发生了大幅度的荧光红移。在这些化合物中，πph的能级可以在不影响πtpy和π*tpy能级的情况下进行调控，这为调节荧光颜色提供了一种新方法。
• Double-helical complexes from simple 2,2′ : 6′,2″-terpyridines; the crystal and molecular structure [Cu₂(Ph₂tpy)₂][PF₆]₂(Ph₂tpy = 6,6″-diphenyl-2,2′ : 6′,2″-terpyridine)
  作者：Edwin C. Constable、Andrew J. Edwards、Michael J. Hannon、Paul R. Raithby

  DOI：10.1039/c39940001991

  日期：——

  2,2′:6′,2″-Terpyridines from dinuclear complexes with copper(I) which are double-helical; the introduction of 6-phenyl substituents stabilises the helicate, and the crystal and molecular structure of [Cu2(Ph2tpy)2][PF6]2 described.

  2,2′:6′,2″-吡啶双配体从含有双核铜(I)的双螺旋复合物中得到；引入6-苯基取代基稳定了螺旋体，并描述了[Cu2(Ph2tpy)2][PF6]2的晶体和分子结构。
• Silver(I)-2,2′:6′2′-terpyridine complexes: X-ray structure of [{Ag(tpy)(MeCN)}2][PF6]2 and [Ag(dptpy)(MeCN)][BF4]·MeCN (tpy = 2,2′: 6′2′-terpyridine; dptpy = 6,6′-diphenyl-2,2′:6′,2′-terpyridine)
  作者：Edwin C. Constable、Andrew J. Edwards、Geoffrey R. Haire、Michael J. Hannon、Paul R. Raithby

  DOI：10.1016/s0277-5387(97)00333-1

  日期：1998.1

  silver(I) acetate with 2,2′: 6′,2′-terpyridine (tpy) and 6,6′-diphenyl-2,2′: 6′, 2′-terpyridine (dptpy) has been investigated. In contrast to the behaviour with copper(I), no dinuclear double-helical species have been unambiguously isolated although there is evidence that double-helical [Ag2L2]2+ complexes exist in weakly-coordinating solvents. In the case of 2,2′ : 6′,2′-terpyridine, a species containing

  摘要乙酸银（I）与2,2'：6'，2'-吡啶（tpy）和6,6'-diphenyl-2,2'：6'，2'-吡啶（dptpy）的配位作用调查。与铜（I）的行为相反，尽管有证据表明弱配位溶剂中存在双螺旋[Ag2L2] 2+络合物，但没有明确分离出双核双螺旋物质。对于2,2'：6'，2'-三联吡啶，已分离出一种包含方形[Ag（tpy）（MeCN）] +阳离子的物种，其结构特征在于上升，而6,6'-二苯基- 2,2'：6'2'：-trepyridine一个相关但非常扭曲的[Ag（dptpy）（MeCN）] +物种已在结构上得到了表征。
• Direct synthesis of disubstituted aromatic polyimine chelates
  作者：C.O. Dietrick-Buchecker、P.A. Marnot、J.P. Sauvage

  DOI：10.1016/s0040-4039(00)85821-9

  日期：1982.1

  The reaction of an alkyl- or aryl-lithium with 1,10-phenanthroline followed by hydrolysis and rearomatisation with manganese dioxide gives good yields of the 2,9-disubstituted product. This synthetic method has been extended to other polyimines such as 2,2′-bipyridine, 2,2′,6′, 2″-terpyridine and 1,8-naphtyridine.

  烷基锂或芳基锂与1,10-菲咯啉的反应，然后水解和用二氧化锰重新芳构化，可以得到2,9-二取代产物的良好收率。该合成方法已扩展到其他聚亚胺，例如2,2'-联吡啶，2,2'，6'，2''-叔吡啶和1,8-萘啶。
• Dietrich-Buchecker, C. O.; Marnot, P. A.; Sauvage, J. P., Nouveau Journal de Chimie, 1984, vol. 8, p. 573 - 582
  作者：Dietrich-Buchecker, C. O.、Marnot, P. A.、Sauvage, J. P.、Kintzinger, J. P.、Maltese, P.

  DOI：——

  日期：——