[2-bromo-3,7,8,12,13,17,18-heptakis(octylsulfanyl)-5,10,15,20-porphyrazinato]nickel(II) | 1146970-03-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: [2-bromo-3,7,8,12,13,17,18-heptakis(octylsulfanyl)-5,10,15,20-porphyrazinato]nickel(II)
• CAS: 1146970-03-7
• 化学式: C₇₂H₁₁₉BrN₈S₇*Ni
• 分子量: 1459.85
• InChiKey: DRZYFHLSHVQJRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  26.29
• 重原子数：
  89.0
• 可旋转键数：
  56.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  105.54
• 氢给体数：
  0.0
• 氢受体数：
  13.0

反应信息

• 作为反应物：
  描述：

  [2-bromo-3,7,8,12,13,17,18-heptakis(octylsulfanyl)-5,10,15,20-porphyrazinato]nickel(II) 、 4-联苯硼酸 在 四(三苯基膦)钯 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 4.0h， 以50%的产率得到[2-(biphenyl-4-yl)-3,7,8,12,13,17,18-heptakis(octylsulfanyl)-5,10,15,20-porphyrazinato]nickel(II)
  参考文献：
  名称：

  Columnar Discotic Mesophases from Novel Non-symmetrically Substituted (Octylsulfanyl) Porphyrazines

  摘要：

  Synthesis and mesomorphism of novel non-symmmetric mono beta-aryl (octylsulfanyl)porphyrazines and their Ni(II) complexes were reported. A recently disclosed asymmetrization procedure led to mono beta-bromo substituted porphyrazines, which provided access to aryl substituted derivatives through Suzuki cross-coupling. UV-Vis spectroscopy showed a bathochromic shift for bromine and aryl substituted nickel complexes. Optical Microscopy and DSC showed that Br derivatives 3a-3b and H-heptakis Ni(II) complex 2b display two columnar mesophases (Col(h) and Col,) stable even at RT and a wide Delta T (100 degrees C). Introduction of the aryl substituent on the macrocycle caused the appearance of only the Col(h) mesophase and lower Delta T.

  DOI：

  10.1080/15421400701834088
• 作为产物：
  描述：

  [3,7,8,12,13,17,18-heptakis(octylsulfanyl)-5,10,15,20-porphyrazinato]nickel(II) 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 氯仿 为溶剂， 反应 0.25h， 生成 [2-bromo-3,7,8,12,13,17,18-heptakis(octylsulfanyl)-5,10,15,20-porphyrazinato]nickel(II)
  参考文献：
  名称：

  Columnar Discotic Mesophases from Novel Non-symmetrically Substituted (Octylsulfanyl) Porphyrazines

  摘要：

  Synthesis and mesomorphism of novel non-symmmetric mono beta-aryl (octylsulfanyl)porphyrazines and their Ni(II) complexes were reported. A recently disclosed asymmetrization procedure led to mono beta-bromo substituted porphyrazines, which provided access to aryl substituted derivatives through Suzuki cross-coupling. UV-Vis spectroscopy showed a bathochromic shift for bromine and aryl substituted nickel complexes. Optical Microscopy and DSC showed that Br derivatives 3a-3b and H-heptakis Ni(II) complex 2b display two columnar mesophases (Col(h) and Col,) stable even at RT and a wide Delta T (100 degrees C). Introduction of the aryl substituent on the macrocycle caused the appearance of only the Col(h) mesophase and lower Delta T.

  DOI：

  10.1080/15421400701834088

文献信息

• Non-symmetrical aryl- and arylethynyl-substituted thioalkyl-porphyrazines for optoelectronic materials: synthesis, properties, and computational studies
  作者：Sandra Belviso、Mario Amati、Rocco Rossano、Alessandra Crispini、Francesco Lelj

  DOI：10.1039/c4dt03317e

  日期：——

  A series of novel non-symmetrically substituted mono β-aryl and β-arylethynyl (alkylsulfanyl)porphyrazines and the corresponding Ni(II) complexes have been prepared by the Suzuki–Miyaura and Sonogashira cross-coupling reactions with the aim to investigate substituent effects on their electronic and aggregation properties. Spectroscopic, electrochemical and computational investigations show that in

  Suzuki-Miyaura和Sonogashira交叉偶联反应制备了一系列新型非对称取代的单β-芳基和β-芳基乙炔基（烷基硫烷基）卟啉和相应的Ni（II）配合物，目的是研究取代基对它们的电子和聚集特性。光谱，电化学和计算研究表明，在芳基和芳基乙炔基化合物中，芳基和大环部分之间均发生有效的电子转移。强烈的给电子（NMe 2）和吸电子（NO 2）提供了卟啉π电子核的最高扰动）芳基取代基，分别增加和降低大环电子密度。而且，尽管在大多数化合物中，LUMO和HOMO主要位于卟啉环上，但是在氨基取代的衍生物中，HOMO位于周边的芳基部分上，而LUMO位于大环上。电荷转移电子激发引起氨基和硝基取代化合物在UV-Vis光谱中的吸收。在前者中，这种激发发生在芳基定位到大环定位的轨道上，而后一种激发发生在芳基定位的轨道上。因此，卟啉嗪环表现出矛盾的行为，在NMe 2取代的化合物中起电子受体的作用，在NO 2