八(甲硫基)四氮杂卟啉锌(II) | 101551-84-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 八(甲硫基)四氮杂卟啉锌(II)
• 英文名称: octakis(methylthio)tetraazaporphyrinzinc(II)
• 英文别名: ZINC;4,5,9,10,14,15,19,20-octakis(methylsulfanyl)-2,7,12,17,21,23-hexaza-22,24-diazanidapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1,3,5,7,9,11(23),12,14,16,18(21),19-undecaene
• CAS: 101551-84-2
• 化学式: C₂₄H₂₄N₈S₈Zn
• 分子量: 746.426
• InChiKey: RNXHELGWIBTJHT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.14
• 重原子数：
  41
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  279
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  ammonium hexafluorophosphate 、 顺-双(2,2-二吡啶)二氯化钌(II) 水合物 、 八(甲硫基)四氮杂卟啉锌(II) 以 甲醇 、 苯 为溶剂， 以81%的产率得到[zinc(II)(octakis(methylthio)tetraazaporphyrin(2-))][Ru(2,2'-bipyridine)2][PF6]2
  参考文献：
  名称：

  Synthesis, spectral and excited state energy transfer studies on new supramolecular ruthenium polypyridyl triads with octakis(methylthio)tetraazaporphyrinzinc(II)

  摘要：

  New bichromophoric di- and trinuclear complexes were synthesized through coordinate strapping of one or two (bay)(2)Ru-II/(phen)(2)Ru-II/Cp(PPh3)Ru-II moieties to [Zn{(MeS)(8)TAP}] 1, core. Thus five new complexes of the type [Zn{(MeS)(8)TAP}{Ru(bpy)(2)}][PF6](2) 2, bent and linear [Zn{(MeS)(8)TAP}{Ru(bpy)(2)}{Ru(phen)(2)}][PF6](4) 3 and 4, bent and linear [Zn{(MeS)(8)TAP}{Ru(bpy)(2)}(RuCp(PPh3)}][PF6](3) 5 and 6, were synthesized and characterized using IR, H-1 NMR, UV-visible, and mass spectral data. The trinuclear complexes 3-6 possessed bent (kappa(4)-S-2,S-3,S-7,S-11)[Ru-II](2) and linear (kappa(4)-S-2,S-3,S-12,S-13)[Ru-II](2) arrangements of the peripheral metallo-chromophore units. Unlike the two reversible reduction waves in complex 1 observed at E-1/2 -0.34 and -0.60 V, only one reversible reduction wave was observed, between E1/2 -0.56 to -0.58 V vs. Ag/AgCl, in the di- and trinuclear complexes 2-6. Also in the anodic scans, the dinuclear complexes 2, as well as linear trinuclear complexes 4 and 6, exhibited two Successive one electron oxidations, the first at E-1/2 similar to 0.62 V due to Ru(II)/Ru(III) process and second at E-1/2 similar to 1.16 V vs. Ag/AgCl due to {(MeS)(8)TAP}/{(MeS)(8)TAP}(+) processes, while the bent trinuclear complexes 3 and 5 exhibited three successive one electron oxidations, i.e. one additional oxidation wave at E-1/2 0,88 and 0.90 V vs. Ag/AgCl, respectively. In the fluorescence measurements, Soret excitation led to strong [Zn{(MeS)(8)TAP}] centered S-2 emission together with a rapid intercomponent excitation energy transfer (k 10(7)-10(8) s(-1)) to peripheral Ru(II) unit that showed emission maxima between 535 and 545 run. Lifetime analysis showed that Ru(II)(+) emission predominated in the dinuclear complex 2, but its contribution dropped significantly upon formation of the trinuclear complexes, which has been explained in terms of relative variation of the LUMO energies of the linked chromophores in the excited states. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2008.12.062
• 作为产物：
  描述：

  cis-1,2-bis-(methylmercapto)-1,2-dicyanoethylene 在 zinc diacetate 、 对甲苯磺酸 、 六甲基二硅氮烷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以35%的产率得到八(甲硫基)四氮杂卟啉锌(II)
  参考文献：
  名称：

  在温和条件下高效一锅法合成金属卟啉

  摘要：

  通过在 120 °C 的 DMF 中用金属盐、六甲基二硅氮烷 (HMDS) 和对甲苯磺酸 (PTSA) 处理，首次实现了从马来腈中制备游离碱和金属四氮杂卟啉的新型单步法。该反应为在温和条件下直接合成具有多种金属和取代马来腈的金属卟啉提供了一种新的制备方法。

  DOI：

  10.1055/s-2006-944186

文献信息

• Efficient synthesis of metallated thioporphyrazines in task specific ionic liquids and their spectroscopic investigation of binding with selected transition metal ions
  作者：POONAM、RITIKA NAGPAL、SMRITI ARORA、SHIVE M S CHAUHAN

  DOI：10.1007/s12039-016-1143-8

  日期：2016.9

  nature and deserve serious attention in the area of design of effective separation and efficient micro-sensing techniques. The UV–Vis absorption spectroscopy and fluorescence signalling are mainly used to study peripheral binding of transition metal ions. Tetramerization of substituted maleonitriles in task specific 2-hydroxylethyl based imidazolium ionic liquids at 120°C gave corresponding thioporphyrazines

  在120∘时基于任务特定的2-羟乙基乙基咪唑鎓离子液体中的取代马来腈的四聚C以中等收率得到相应的富电子的外围取代的硫代卟啉嗪。与非羟基官能化的离子液体相比，2-羟乙基咪唑鎓离子液体的收率更高。此外，这些含硫的外围官能化的卟啉嗪用于光谱研究与钯（II）和汞（II）离子的结合研究。这些金属离子本质上是有毒的，在有效分离和有效微传感技术的设计领域中应引起高度重视。UV-Vis吸收光谱和荧光信号主要用于研究过渡金属离子的外围结合。 在120°C下，基于任务特定的2-羟乙基乙基咪唑鎓离子液体的取代马来腈四聚，得到相应的硫代卟啉嗪，收率适中。含硫的外围功能化的卟啉嗪用于光谱研究与钯（II）和汞（II）离子的结合研究。主要使用UV-Vis吸收光谱法和荧光信号传导法，因为这些技术高度敏感且易于区分与此类金属结合研究相关的化学和物理变化。
• Microwave-assisted synthesis of metalloporphyrazines
  作者：M. Chandrasekharam、Ch. Srinivasa Rao、Surya P. Singh、M. Lakshmi Kantam、M. Ramesh Reddy、P. Yella Reddy、T. Toru

  DOI：10.1016/j.tetlet.2007.02.007

  日期：2007.4

  The synthesis of metalloporphyrazines with enhanced yields directly from substituted maleonitriles is described. The one-step procedure involves tetramerization using hexamethyldisilazane, p-toluenesulfonic acid and DMF in a sealed tube under microwave irradiation. The reaction time has been drastically reduced from 24 h by classical oil-bath heating to just 15 min. (c) 2007 Elsevier Ltd. All rights reserved.