hemiporphyrazine | 343-44-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: hemiporphyrazine
• 英文别名: Hemiporphyrazin；2,8,17,23,31,32,33,34-Octazaheptacyclo[22.6.1.13,7.19,16.118,22.010,15.025,30]tetratriaconta-1(31),2,4,6,8,10,12,14,16(33),17,19,21,23,25,27,29-hexadecaene；2,8,17,23,31,32,33,34-octazaheptacyclo[22.6.1.13,7.19,16.118,22.010,15.025,30]tetratriaconta-1(31),2,4,6,8,10,12,14,16(33),17,19,21,23,25,27,29-hexadecaene
• CAS: 343-44-2
• 化学式: C₂₆H₁₆N₈
• 分子量: 440.467
• InChiKey: KWHQDNKVVVTPFL-UHFFFAOYSA-N

物化性质

• 沸点：
  810.4±60.0 °C(Predicted)
• 密度：
  1.470±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  34
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  98.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  hemiporphyrazine 在 水 作用下， 以 苯甲醇 为溶剂， 反应 2.0h， 以98%的产率得到5,26:13,18-diimino-7,11:20,24-dinitrilo-dibenzo{c,n}-1,6,12,17-tetraazacyclodocosine hydrate
  参考文献：
  名称：

  Excitonic Luminescence of Hemiporphyrazines

  摘要：

  Metal-free hemiporphyrazine (HpH(2)) is a notoriously insoluble material possessing interesting photophysical properties. Here we report the synthesis, structure, and photophysical properties of an octahedral zinc trans-ditriflate hemiporphyrazine complex "HpH(2)Zn(OTf)(2)" that contains a neutral hemiporphyrazine ligand. The photophysical properties of hemiporphyrazine are largely unaffected by introduction of zinc(II) triflate, but a dramatic increase in solubility is observed. HpH(2)Zn(OTf)(2) therefore provides a convenient model system to evaluate the impact of aggregation on the photophysical properties of hemiporphyrazine. Soluble aggregates and crystalline materials containing planar hemiporphyrazines exhibit relatively strong absorbance of visible light (450-600 nm) and red luminescence (600-700 nm). Hemiporphyrazine monohydrate (HpH(2)center dot H2O), in contrast, has a nonplanar "saddle-shaped" conformation that exhibits very little absorbance of visible light in solution or in the solid state. Upon photoexcitation at 380 nm, HpH(2)Zn(OTf)(2) and HpH(2) exhibit multiwavelength emissions centered at 450 and 650 nm. Emissions at 450 nm are highly anisotropic, while emissions at 650 nm are fully depolarized with respect to a plane-polarized excitation source. Taken together, our results suggest that excitonic coupling of aggregated and crystalline hemiporphyrazines results in increased absorbance and emission of visible light from S-0 <-> S-1 transitions that aye usually symmetry forbidden in isolated species. In contrast to previously proposed theories involving excited-state intramolecular proton transfer, we propose that the multiple-wavelength luminescent emissions of HpH(2)Zn(OTf)(2) and HpH(2) are due to emissive S-1 and S-2 states in aggregated and crystalline hemiporphyrazines. These results may provide a better understanding of the nonlinear optical properties of these materials in solution and in the solid state.

  DOI：

  10.1021/ic2017566
• 作为产物：
  描述：

  1,2-二氰基苯 在 甲醇 、 氨 作用下， 生成 hemiporphyrazine
  参考文献：
  名称：

  975.杂环亚胺。第一部分。异吲哚啉的氨基衍生物及其与伯碱的反应

  摘要：

  DOI：

  10.1039/jr9520005000

文献信息

• C–H bond activation and ring oxidation in nickel carbahemiporphyrazines
  作者：Saovalak Sripothongnak、Natalie Barone、Christopher J. Ziegler

  DOI：10.1039/b909871b

  日期：——

  The first nickel complexes of two carbon-substituted phthalocyanine analogues are reported; both exhibit direct Ni–C bonding and oxygen activation chemistry is observed.

  报道了两种碳取代的酞菁类似物的首个镍配合物；两者都表现出直接的Ni–C键合，并且观察到了氧活化化学反应。
• Microwave-assisted synthesis and sublimation enthalpies of hemiporphyrazines
  作者：Aleksandra S. Kuznetsova、Nadezhda L. Pechnikova、Yuriy A. Zhabanov、Aleksey E. Khochenkov、Oscar I. Koifman、Victor V. Aleksandriiskii、Mikhail K. Islyaikin

  DOI：10.1142/s1088424619500263

  日期：2019.3

  It was established that microwave irradiation solvent-free processing of 2,6- diaminopyridine or 1,3-phenylenediamine with phthalonitrile or 4-tert-butylphthalonitrile led to corresponding hemiporphyrazines with sufficiently high yields and a huge reduction in the time required for synthesis, from 8–12 h to 20 min. The data of IR and UV-vis spectroscopies and elemental analysis of the final products were found to be similar to those described in literature. The obtained hemiporphyrazines were characterized by ¹H and [Formula: see text]C NMR data. We applied the Knudsen effusion method with mass spectrometric control of vapor composition. The mass spectrometric investigations established that the macrocyclic compounds give a stable stream of particles and their enthalpies of sublimation were estimated by the second law of thermodynamics.

  研究发现，用微波辐照无溶剂处理 2,6- 二氨基吡啶或 1,3- 苯二胺与邻苯二腈或 4-叔丁基邻苯二腈，可得到相应的半卟嗪类化合物，而且产率足够高，合成时间也大大缩短，从 8-12 小时缩短到 20 分钟。最终产物的红外光谱、紫外光谱和元素分析数据与文献中描述的相似。获得的半卟嗪类化合物通过 1H 和[式：见正文]C NMR 数据进行了表征。我们采用克努森流出法对蒸汽成分进行质谱控制。质谱分析表明，大环化合物能产生稳定的粒子流，其升华焓是根据热力学第二定律估算的。
• Synthesis, structure, and magnetic properties of catena-(.mu.-oxo)(hemiporphyrazinato)iron(IV), the first polymeric .mu.-oxo-bridged complex of iron
  作者：Wolfgang Hiller、Joachim Straehle、Armin Datz、Michael Hanack、William E. Hatfield、Leonard W. Ter Haar、Philipp Guetlich

  DOI：10.1021/ja00314a013

  日期：1984.1

  Abstract : The crystal and molecular structure of the compound catena-micron-oxo-hemiporphyrazinatoiron(IV), (Fe0N8C26H14n), has been determined from single-crystal, three-dimensional X-ray diffraction counter data. The compound crystalizes as blue-black needles in space group P2/n with Z = 2 and having unit cell dimensions (at 210 K) a = 16.090 (3) angstroms, b = 3.975 (2) angstroms, c = 16.070 (3)

  摘要 : 化合物catena-micron-oxo-hemiporphyrazinatoiron (IV), (Fe0N8C26H14n) 的晶体和分子结构已从单晶、三维X 射线衍射计数器数据确定。该化合物在空间群 P2/n 中结晶为蓝黑色针状晶体，Z = 2，晶胞尺寸（210 K）a = 16.090 (3) 埃，b = 3.975 (2) 埃，c = 16.070 (3)和 beta = 92.97 (1)。通过全矩阵最小二乘法将结构细化到常规 R 值为 0.054。扭曲的半卟啉单元沿 b 轴堆叠，并通过轴向结合的氧桥连接成聚合的、均匀间隔的线性链。氧原子被无序地分成两个晶体学上不同的位点，这些位点位于一个中心位置，该位置垂直于与链共线的 C2 轴。Fe-0-Fe 角为 158.2 和 170.5，Fe-0 键距范围从 1.973 埃到 2.030 埃，穆斯堡尔谱研究在 4.2 K、室温和
• Sandwich rare earth complexes simultaneously involving aromatic phthalocyanine and antiaromatic hemiporphyrazine ligands showing a predominantly aromatic nature
  作者：Wenbo Liu、Houhe Pan、Ziqian Wang、Kang Wang、Dongdong Qi、Jianzhuang Jiang

  DOI：10.1039/c7cc01279a

  日期：——

  Two mixed (phthalocyaninato)(hemiporphyrazinato) and two homoleptic bis(hemiporphyrazinato) rare earth double-decker complexes have been synthesized and structurally characterized. The EPR and NMR results clarified the protonated nature of these sandwich double-deckers....

  合成了两种混合的（酞菁基）（hemiporphyrazinato）和两种均化的双（hemiporphyrazinato）稀土双层配合物，并对其结构进行了表征。EPR和NMR结果阐明了这些三明治双层分子的质子化性质。
• Hemiporphyrazine-Involved Sandwich Dysprosium Double-Decker Single-Ion Magnets
  作者：Wenbo Liu、Suyuan Zeng、Xin Chen、Houhe Pan、Dongdong Qi、Kang Wang、Jianmin Dou、Jianzhuang Jiang

  DOI：10.1021/acs.inorgchem.8b02068

  日期：2018.10.1

  for the dysprosium ion and ensures the strengthened magnetic properties of both single-ion magnets (SIMs) in terms of coordination geometry. Magnetic studies reveal that both double-deckers exhibit typical SIM behavior with a spin reversal energy barrier of 80.1 ± 6.3 K for 1 and 57.3 ± 3.8 K for 2 as well as the hysteresis loops emerging at 3 K. In particular, introduction of two Hp ligands with four

  杂配的（phthalocyaninato）（hemiporphyrazinato）和均配的bis（hemiporphyrazinato）s双层复合物Dy [H（Hp）2 ]（1）和Dy [H（Pc）（Hp）]（2）（H 2 Pc =无金属酞菁； H 2Hp =无金属的半卟啉（Hp），是经过设计，合成和结构表征的。两个双层中的dy中心都与八角坐标相协调，具有接近理想的正方形-反棱柱形配位几何形状，这为an离子提供了更大的分子各向异性，并确保了两个单离子磁体（SIM）的增强的磁性能。协调几何。磁性研究表明，两个双层汽车均具有典型的SIM行为，自旋反转能垒分别为1和87.3±6.3 K，2为57.3±3.8 K，以及出现在3 K的磁滞回线。特别是引入了两个Hp与four自旋中心配位的具有四个吡啶氮原子的配体赋予Dy [H（Hp）2 ]（1）在具有N 4-大环配体的夹心型SIM SIM中具有迄今为