11,12-dibromo-dipyrido[3,2-a:2',3'-c]-phenazine | 894354-38-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 11,12-dibromo-dipyrido[3,2-a:2',3'-c]-phenazine
• 英文别名: 11,12-Dibromoquinoxalino[2,3-f][1,10]phenanthroline
• CAS: 894354-38-2
• 化学式: C₁₈H₈Br₂N₄
• 分子量: 440.096
• InChiKey: JPTOFZYSIYEEEZ-UHFFFAOYSA-N

物化性质

• 沸点：
  656.7±50.0 °C(Predicted)
• 密度：
  1.903±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  11,12-dibromo-dipyrido[3,2-a:2',3'-c]-phenazine 、 4-硼酸三苯胺 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 potassium carbonate 作用下， 以 乙醇 、 水 、 甲苯 为溶剂， 以78%的产率得到11,12-di(4-diphenylaminophenyl)dipyrido[3,2-a:2′,3′-c]-phenazine
  参考文献：
  名称：

  配体Re-dppz复合物中扭转连接的配体内供体-受体相互作用的改变。

  摘要：

  一系列[ReCl（CO）3（dppz）]研究了具有取代供体基团的配合物。通过扭转角和给体取代基的数量和性质的调节改变供体-受体的通讯，可以通过计算和光谱技术，包括依赖于时间的密度泛函理论和共振拉曼光谱和时间拉曼光谱来表征对光物理性质的影响。分辨红外光谱。由于施主基团的调制，基态光学性质显示出显着变化，施主基团与受主基团之间的夹角增加，蓝移并耗尽了最低能量跃迁的强度，这始终是配体中的配体内电荷转移（ILCT）自然。但是，在所有研究的络合物中，对激发态性质和动力学的扰动最小。1个ILCT，3个ππ*和3个ILCT。

  DOI：

  10.1021/acs.inorgchem.7b01710
• 作为产物：
  描述：

  N,N’-二(对甲苯磺酰基)-1,2-苯二胺 在 硫酸 、 溴 、 potassium carbonate 、 溶剂黄146 作用下， 以 乙醇 、 水 为溶剂， 反应 12.0h， 生成 11,12-dibromo-dipyrido[3,2-a:2',3'-c]-phenazine
  参考文献：
  名称：

  双取代RuII Dppz类似物的光驱动多电子存储

  摘要：

  制备了叠层受体配体二吡啶基-[3,2--a：2'，3'-c]吩嗪（dppz）的四种衍生物及其相应的钌配合物[Ru（phen）2（dppzX 2）] 2+。并通过NMR光谱，ESI-MS和元素分析进行​​表征。新的配体（通常表示为dppzX 2）在远端苯环上对称地双取代，得到10,13-dibromodppz（dppz- p -Br），11,12-dibromodppz（dppz- o -Br），10,13-dicyanodppz （dppz- p -CN），11,12-二氰基-dcyanzpppp（dppz- o‐CN）。钌配合物的溶剂化基态MO计算表明，这些吸电子取代基不仅降低了dppz配体的LUMO（dppz（CN）2

  DOI：

  10.1002/chem.201502607

文献信息

• Mechanochemical Synthesis, Photophysical Properties, and X-ray Structures of N-Heteroacenes
  作者：Prasit Kumar Sahoo、Chandan Giri、Tuhin Subhra Haldar、Rakesh Puttreddy、Kari Rissanen、Prasenjit Mal

  DOI：10.1002/ejoc.201600005

  日期：2016.3

  chromatographic purifications could be avoided after the solvent-free syntheses. The UV/Vis absorption spectra of the pyrazaacenes show intense absorption bands in the near-IR region. The single-crystal X-ray analyses of selected pyrazaacene derivatives showed pairwise π–π interactions and some C–H···π interactions, which could account for some of the photophysical features of the compounds in the solid

  所描述的机械化学方法是概念验证的一个例子，在该方法中，在无溶剂球磨条件下实现了基于溶液的乏味、收率低且困难的吡氮杂并苯合成；该方法简单、高产、省时、环保。合成的化合物还包括吡氮杂并苯（N-杂并苯），它们是含有芘结构单元的辛苯类似物。该化合物微溶于普通溶剂，无溶剂合成后可避免柱层析纯化。吡氮杂并苯的紫外/可见吸收光谱在近红外区域显示出强烈的吸收带。选定的吡氮杂并苯衍生物的单晶 X 射线分析显示成对的 π-π 相互作用和一些 C-H…π 相互作用，
• Derivatives of dipyrido[3,2-a:2′,3′-c]phenazine and its ruthenium complexes, influence of arylic substitution on photophysical properties
  作者：Bernhard Schäfer、Helmar Görls、Martin Presselt、Michael Schmitt、Jürgen Popp、William Henry、Johannes G. Vos、Sven Rau

  DOI：10.1039/b512773d

  日期：——

  The synthesis and photophysical properties of a series of substituted dipyridophenazine (dppz) ruthenium complexes of the type [(tbbpy)2Ru(dppz-R2)]2+ (where tbbpy = 4,4-tert-butyl-2,2-bipyridine and dppz = dipyrido[3,2-a:2′,3′-c]phenazine and R represents substitution at the 11 and 12 position with: Br, phenyl, 4-tert-butyl-phenyl and para-biphenyl) are described. The ligands could be obtained in high yields using Suzuki-type coupling reactions, an approach which also has been successfully applied to the analogous dppz-Br2 ruthenium complex. All compounds are fully characterised by NMR, MS and UV-vis spectroscopy. The solid state structures of dppz-bi-para-biphenyl and the ruthenium complex [(tbbpy)2Ru(dppz-Br2)]2+ are also reported. The investigation of the free ligands reveals a pronounced effect of the arylic substitution on absorption and emission properties. These properties are mirrored in the corresponding complexes, which possess emission lifetimes of up to 900 ns. The resonance Raman investigation of the complex [(tbbpy)2Ru(dppz-Br2)]2+ supports the assumption that the excited state properties of the substituted complexes are related to the parent [(bpy)2Ru(dppz)]2+ compound, but that important differences may be expected based on the differences observed in the lowest energy absorption band.

  本文描述了一系列取代二吡啶并吡嗪（dppz）钌配合物（类型为[(tbbpy)2Ru(dppz-R2)]2+，其中tbbpy=4,4-叔丁基-2,2-联吡啶，dppz=二吡啶并[3,2-a:2⁺,3⁺-c]并吡嗪，R代表在11和12位上的取代基：溴、苯基、4-叔丁基苯基和对联苯）的合成和光物理性质。使用铃木型偶联反应可以高收率地获得配体，这种方法也成功地应用于类似的dppz-Br2钌配合物。所有化合物均通过核磁共振、质谱和紫外-可见光谱进行了充分表征。还报告了dppz-双对联苯和钌配合物[(tbbpy)2Ru(dppz-Br2)]2+的固态结构。对游离配体的研究揭示了芳基取代对吸收和发射性质的影响。这些性质在相应的配合物中得到了反映，其发射寿命可达900ns。对配合物[(tbbpy)2Ru(dppz-Br2)]2+的共振
• Synthesis, evaluation of biological activity studies of iridium(III) complexes against human gastric carcinoma SGC-7901 cells
  作者：Yi Zhou、Lan Bai、Yi-Ying Gu、Li Tian、Hui Yin、Yuan-Yuan Zhang、Hui-Wen Zhang、De-Gang Xing、Yun-Jun Liu

  DOI：10.1016/j.inoche.2020.108012

  日期：2020.8

  Three new iridium(III) complexes [Ir(ppy)(2)(DBDPPZ)](PF6) (1), [Ir(bzq)(2)(DBDPPZ)](PF6) (2) and [Ir(piq)(2)(DBDPPZ)](PF6) (3) were synthesized and characterization. The cytotoxicity in vitro of the complexes against several cancer cells was evaluated by MTT method. The complexes show high anticancer activity against MDA-DB231, SGC-7901, A549 and HeLa cells. In particular, complexes 1, 2 and 3 exhibit very high cytotoxic effect on SGC-7901 cells with a very low IC50 value of 1.53 +/- 0.10, 0.17 +/- 0.05 and 0.30 +/- 0.03 mu M, respectively. The cell colonies formation, intracellular ROS, mitochondrial membrane potential, intracellular Ca2+ levels were investigated under fluorescence microscope. Studies show that the complexes can inhibit cell colonies formation, increase intracellular ROS and Ca2+ levels, induce a decrease in the mitochondrial membrane potential. The apoptosis and cell cycle arrest were also studied by flow cytometry. Additionally, the complexes can regulate the expression of caspase 3 and Bcl-2 family proteins. Taken together, the complexes induce apoptosis in SGC-7901 cells through a ROS-mediated mitochondrial dysfunction pathway.
• Re(I) Complexes of Substituted dppz: A Computational and Spectroscopic Study
  作者：Holly van der Salm、Michael G. Fraser、Raphael Horvath、Scott A. Cameron、Jonathan E. Barnsley、Xue-Zhong Sun、Michael W. George、Keith C. Gordon

  DOI：10.1021/ic403056g

  日期：2014.3.17

  A series of dipyrido[3,2-a:2',3'-c]phenazine (dppz)-based ligands with electron-withdrawing substituents and their [Re(CO)(3)(L)Cl] and [Re(CO)(3)(L)(py)]PF6 complexes have been studied using Raman, resonance Raman, and transient resonance Raman (TR2) and time-resolved infrared (TRIR) spectroscopic techinques in conjunction with computational chemistry as well as electrochemical studies, emission, and absorption of ground and excited states. DFT (B3LYP) frequency calculations show good agreement with nonresonant Raman spectra, which allowed these to be used to identify phenanthroline, phenazine, and delocalized modes. These band assignments were used to establish the nature of chromophores active in resonance Raman spectra, probed with wavelengths between 350.7 and 457.9 nm. X-ray crystallography of [Re(CO)(3)(dppzBr(2))Cl] and [Re(CO)(3)(dppzBr)(py)PF6 showed these crystallize in space groups triclinic P1 and monoclinic P2(1/n), respectively. Electrochemical studies showed that substituents have a strong effect on the phenazine MO, changing the reduction potential by 200 mV. Transient absorption studies showed that generally the [Re(CO)(3)(L)(py)]PF6 complexes had longer lifetimes than the corresponding [Re(CO)(3)(L)Cl] complexes; the probed state is likely to be pi -> pi* (phz) in nature. TR2 spectra of the ligands provided a marker for the triplet pi -> pi* state, and the TR2 spectra of the complexes suggest an intraligand (IL) pi,pi* state for [Re(CO)(3)(L)(py)](+) complexes, and a potentially mixed IL/MLCT state for [Re(CO)(3)(L)Cl] complexes. TRIR spectroscopy is more definitive with THEXI state assignments, and analysis of the metal-carbonyl region (1800-2100 cm(-1)) on the picosecond and nanosecond time scales indicates the formation of MLCT(phen/phz) states for all [Re(CO)(3)(L)Cl] complexes, and IL pi -> pi* (phen) states for all [Re(CO)(3)(L)(py)](+) complexes, with all but [Re(CO)(3)(dppzBr(CF3))(py)(+) showing some contribution from an MLCT(phen) state also.