tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine | 832747-42-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine
• 英文别名: tetrakis[2,3-(5,6-di-2-pyridylpyrazino)porphyrazine]；Py8TPyzPzH2；6,7,15,16,24,25,33,34-Octapyridin-2-yl-2,5,8,11,14,17,20,23,26,29,32,35,37,38,39,40-hexadecazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28(38),30(37),31,33,35-nonadecaene；6,7,15,16,24,25,33,34-octapyridin-2-yl-2,5,8,11,14,17,20,23,26,29,32,35,37,38,39,40-hexadecazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28(38),30(37),31,33,35-nonadecaene
• CAS: 832747-42-9
• 化学式: C₆₄H₃₄N₂₄
• 分子量: 1139.13
• InChiKey: FDUWOWPAARCYNO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  88
• 可旋转键数：
  8
• 环数：
  17.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  315
• 氢给体数：
  2
• 氢受体数：
  22

反应信息

• 作为反应物：
  描述：

  tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine 在 吡啶 、 cadmium(II) acetate dihydrate 作用下， 反应 4.0h， 以58%的产率得到[Cd(tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazinato)]
  参考文献：
  名称：

  Tetra-2,3-pyrazinoporphyrazines with Externally Appended Pyridine Rings. 8. Central (Zn^II, Cu^II, Mg^II(H₂O), Cd^II) and Exocyclic (Pd^II) Metal Ion Binding in Heteropentametallic Complexes from Tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine

  摘要：

  A series of heteropentametallic porphyrazine macrocycles represented as [(PdCl2)(4)LM], where L = dianion of tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine and M = Zn-II, Cu-II Mg-II(H2O) or Cd-II, were prepared by reaction of the corresponding mononuclear [LM] species, and their behavior was examined by UV-visible and NMR spectroscopy, electrochemistry, and thin layer spectroelectrochemistry in nonaqueous media. The PdCl2 units in [(PdCl2)(4)LM] are coordinated at the pyridine N atoms of the external dipyridinopyrazine fragments ("py-py" coordination) and are displaced out of the plane of the central pyrazinoporphyrazine macrocycle as verified by H-1 and C-13 NMR data on [(PdCl2)(4)LZn]. The same arrangement is also strongly suggested by similar NMR data on the Mg-II and Cd-II analogues. The predominant component in the synthesized materials among the four predictable macrocyclic isomers has the four exocyclic N2(py)PdCl2 square planar coordination sites on the same side of the central macrocyclic framework (4:0 isomer, C-4v symmetry), and this is accompanied by a minor isomeric component (2:2 cis or trans), in line with previous findings on the pentapalladated species [(PdCl2)(4)LPd], IR, UV-visible, and NMR spectral data also provide evidence for transmetalation reactions of the type [(PdCl2)(4)LMg(H2O)] -> [(PdCl2)(4)LPd] and [(PdCl2)(4)LCd] -> [(PdCl2)(4)LPd], with the amount of [(PdCl2)(4)LPd] formed varying from batch to batch. Dissociation of the four exocyclic PdCl2 units from [(PdCl2)(4)LM] occurs in pyridine, but the compounds are stable in N,N-dimethylformamide (DMF) or dimethylsulfoxide (DMSO) and can be stepwise reduced via two one-electron reversible or quasi-reversible processes, prior to an irreversible electroreduction of the bound PdCl2 group at more negative potentials. This metal-centered reduction leads to a [LM](2-) product which is then further reduced to [LM](3-) and [LM](4-) at the electrode surface. The first two reductions of the heteropentametallic compounds are easier than those of the monometallic [LM] species but generally more difficult than reduction of the related octacationic [L'M](8+) derivatives (L' = the octamethylated free-base dianion) whose redox properties were previously reported. The Cd-II octacation [L'Cd](8+), isolated as an iodide salt, was also synthesized for the first time in the current study, and its spectroscopic and electrochemical properties are compared to that of the previously examined analogues.

  DOI：

  10.1021/ic902317h
• 作为产物：
  描述：

  2,3-dicyano-5,6-di(2-pyridyl)pyrazine 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 neat (no solvent) 为溶剂， 以20%的产率得到tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine
  参考文献：
  名称：

  钛基四（2,3- [5,6-二（取代）吡嗪并]卟啉嗪：合成与表征

  摘要：

  通常发现四氮杂卟啉（TPysPz）配体和金属络合物可用作电子材料和催化剂。考虑到钛（Ti）的有限用途，我们制备并表征了四（2,3- [5,6-di-R 8-吡嗪并]卟啉（R = H，2- Py，Ph）。在不同溶剂中进行的UV / Vis测量证实了分子聚集，这在大环边缘存在2-吡啶和苯基取代基的情况下更为明显。由于溶解度低，因此将固态NMR用于结构表征。进行了额外的IR和MALDI-TOF来完成表征。DMSO / Bu 4中的循环伏安法NBF 4 0.1 m宣布我们的钛络合物最多可参加五次氧化还原事件。前两个拟可逆性的还原涉及Ti（IV），而第二个或三个可逆的还原以TPysPz大环为代价。为了测试我们的化合物作为催化材料的适用性，我们在固态下进行了初步的循环伏安法研究，该研究显示了氢氧化还原反应的典型峰。

  DOI：

  10.1002/ejic.202000193

文献信息

• Tetra-2,3-pyrazinoporphyrazines with Externally Appended Pyridine Rings. 5. Synthesis, Physicochemical and Theoretical Studies of a Novel Pentanuclear Palladium(II) Complex and Related Mononuclear Species
  作者：Maria Pia Donzello、Elisa Viola、Xiaohui Cai、Luisa Mannina、Corrado Rizzoli、Giampaolo Ricciardi、Claudio Ercolani、Karl M. Kadish、Angela Rosa

  DOI：10.1021/ic702430j

  日期：2008.5.1

  New palladium(II) complexes of the free-base tetrakis[2,3-(5,6-di-2-pyridylpyrazino)porphyrazine], [Py 8TPyzPzH 2], have been prepared and their physicochemical properties examined. The investigated compounds are the pentanuclear species [(PdCl 2) 4Py 8TPyzPzPd], the monopalladated complex [Py 8TPyzPzPd], and its corresponding octaiodide salt [(2-Mepy) 8TPyzPzPd](I) 8. All three Pd (II) complexes have

  制备了新的游离碱四[2,3-（5,6-二-2-吡啶基吡嗪并）卟啉] [Py 8TPyzPzH 2]钯（II）配合物，并对其理化性质进行了研究。研究的化合物为五核种[（PdCl 2）4Py 8TPyzPzPd]，单palpalated配合物[Py 8TPyzPzPd]及其相应的章鱼碱盐[（2-Mepy）8TPyzPzPd]（I）8。所有三种Pd（II）配合物均具有一个常见的中心吡嗪并卟啉核心，并且仅在大环的外围不同，其中[Py 8TPyzPzPd]中存在的简单二吡啶并吡嗪片段带有四个在五核配合物中的吡啶N原子配位的PdCl 2单元，[（PdCl 2）4Py 8TPyzPzPd] ，或在辛酸[（2-Mepy）8TPyzPzPd]（8+）的碘化物中带有吡啶-N（CH 3）（+）部分。通过一和二阐明了五核配合物[（PdCl 2）4Py 8TPyzPzPd]的结构特征，部分由[（CN）2Py 2PyzPdCl
• Tetra-2,3-pyrazinoporphyrazines with Externally Appended Pyridine Rings. 2. Metal Complexes of Tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine:  Linear and Nonlinear Optical Properties and Electrochemical Behavior
  作者：Maria Pia Donzello、Zoungping Ou、Danilo Dini、Moreno Meneghetti、Claudio Ercolani、Karl M. Kadish

  DOI：10.1021/ic0489084

  日期：2004.12.1

  A series of metal complexes of tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine, [Py(8)TPyzPzH(2)], having the general formula [Py(8)TPyzPzM].xH(2)O (M = Mg(II)(H(2)O), Mn(II), Co(II), Cu(II), Zn(II); x = 3-8) were synthesized by reaction of the free-base macrocycle with the appropriate metal acetate in pyridine or dimethyl sulfoxide under mild conditions. Clathrated water and retained pyridine

  具有通式[Py（8）TPyzPzM]的四[2,3- [5,6-二（2-吡啶基）吡嗪并]卟啉] [Py（8）TPyzPzH（2）]的金属配合物。通过反应合成了xH（2）O（M = Mg（II）（H（2）O），Mn（II），Co（II），Cu（II），Zn（II）; x = 3-8）在温和条件下，在吡啶或二甲基亚砜中用适当的金属乙酸盐制备游离碱大环化合物 Mn（II）和Co（II）物种的笼形水和保留的吡啶分子很容易通过真空加热消除，水分子可通过将未溶剂化的大环化合物暴露于空气中而回收。固态材料的磁化率测量和EPR光谱提供了有关Cu（II），Co（II）和Mn（II）物种自旋态的基本信息。在非供体溶剂（CH（2）Cl（2），CHCl（3）），中等碱性溶剂（吡啶）和酸性溶剂（CH（3）COOH），其聚集程度取决于特定的溶剂和中心金属离子。制备后溶液的UV-vis光谱监测表明，随着时间的推移系统发生
• Tetra-2,3-pyrazinoporphyrazines with peripherally appended pyridine rings. 21. Mono- and pentanuclear FeII complexes: Solid state and solution studies
  作者：Maria Pia Donzello、Elena Puglisi、Claudio Ercolani、Giulia Vozzolo、Jian Rong、Yuanyuan Fang、Karl M. Kadish

  DOI：10.1142/s1088424619502018

  日期：2020.5

  spectroscopy, with added studies on the starting complex [Py8TPyzPzFe] · xH2O regarding magnetic and electrochemical behavior. Clathrated water molecules are present in all compounds and have little to no effect on their physicochemical behavior as was observed for all previously reported analogs. UV-vis spectra of the mononuclear [Py8PyzPzFe] · xH2O complex in DMSO and pyridine are indicative of aggregation

  新铁二式 [Py 8 TPyzPzFe] · xH 2 O，其双吡啶加合物 [Py 8 TPyzPzFe(py) 2 ] · xH 2 O，五核物种 [(MCl2)4Py 8 TPyzPzFe]·xH 2 O (M =钯二, 铂二)和双-DABCO 加合物 [Py 8 TPyzPzFe(DABCO) 2 ] · 11H 2 O 和 [(PdCl2)4Py 8 TPyzPzFe(DABCO) 2 ] · H 2 O (Py 8 TPyzPz =八吡啶并四吡嗪并卟啉二阴离子；达科 =合成了 1,4-二氮杂环[2.2.2]辛烷），并通过元素和热重分析、IR 和 UV-vis 光谱进行了表征，并对起始配合物 [Py 8 TPyzPzFe] · xH 2 O 进行了关于磁性和电化学行为的研究. 笼形水分子存在于所有化合物中，对它们的物理化学行为几乎没有影响，正如之前报道的所有类似物所观察到的那样。单核
• Titanium‐Based Tetrakis‐2,3‐[5,6‐di(Substituted)pyrazino]porphyrazine: Synthesis and Characterization
  作者：Polyssena Renzi、Lucia Mazzapioda、Francesca Nardelli、Francesca Martini、Marco Geppi、Carmine Mancone、Maria Assunta Navarra、Francesca D'Acunzo、Patrizia Gentili

  DOI：10.1002/ejic.202000193

  日期：2020.7.7

  of ligands and Ti‐based complexes of tetrakis‐2,3‐[5,6‐di‐R8‐pyrazino]porphyrazine (R = H, 2‐Py, Ph). UV/Vis measurements in different solvents confirm molecular aggregation, which results more pronounced in the presence of 2‐pyridil and phenyl substituents on the macrocycle edge. Because of low solubility, solid state NMR was applied for structure characterization. Additional IR and MALDI‐TOF were carried

  通常发现四氮杂卟啉（TPysPz）配体和金属络合物可用作电子材料和催化剂。考虑到钛（Ti）的有限用途，我们制备并表征了四（2,3- [5,6-di-R 8-吡嗪并]卟啉（R = H，2- Py，Ph）。在不同溶剂中进行的UV / Vis测量证实了分子聚集，这在大环边缘存在2-吡啶和苯基取代基的情况下更为明显。由于溶解度低，因此将固态NMR用于结构表征。进行了额外的IR和MALDI-TOF来完成表征。DMSO / Bu 4中的循环伏安法NBF 4 0.1 m宣布我们的钛络合物最多可参加五次氧化还原事件。前两个拟可逆性的还原涉及Ti（IV），而第二个或三个可逆的还原以TPysPz大环为代价。为了测试我们的化合物作为催化材料的适用性，我们在固态下进行了初步的循环伏安法研究，该研究显示了氢氧化还原反应的典型峰。
• Tetra-2,3-pyrazinoporphyrazines with Externally Appended Pyridine Rings. 8. Central (Zn^II, Cu^II, Mg^II(H₂O), Cd^II) and Exocyclic (Pd^II) Metal Ion Binding in Heteropentametallic Complexes from Tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine
  作者：Maria Pia Donzello、Elisa Viola、Xiaohui Cai、Luisa Mannina、Claudio Ercolani、Karl M. Kadish

  DOI：10.1021/ic902317h

  日期：2010.3.1

  A series of heteropentametallic porphyrazine macrocycles represented as [(PdCl2)(4)LM], where L = dianion of tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine and M = Zn-II, Cu-II Mg-II(H2O) or Cd-II, were prepared by reaction of the corresponding mononuclear [LM] species, and their behavior was examined by UV-visible and NMR spectroscopy, electrochemistry, and thin layer spectroelectrochemistry in nonaqueous media. The PdCl2 units in [(PdCl2)(4)LM] are coordinated at the pyridine N atoms of the external dipyridinopyrazine fragments ("py-py" coordination) and are displaced out of the plane of the central pyrazinoporphyrazine macrocycle as verified by H-1 and C-13 NMR data on [(PdCl2)(4)LZn]. The same arrangement is also strongly suggested by similar NMR data on the Mg-II and Cd-II analogues. The predominant component in the synthesized materials among the four predictable macrocyclic isomers has the four exocyclic N2(py)PdCl2 square planar coordination sites on the same side of the central macrocyclic framework (4:0 isomer, C-4v symmetry), and this is accompanied by a minor isomeric component (2:2 cis or trans), in line with previous findings on the pentapalladated species [(PdCl2)(4)LPd], IR, UV-visible, and NMR spectral data also provide evidence for transmetalation reactions of the type [(PdCl2)(4)LMg(H2O)] -> [(PdCl2)(4)LPd] and [(PdCl2)(4)LCd] -> [(PdCl2)(4)LPd], with the amount of [(PdCl2)(4)LPd] formed varying from batch to batch. Dissociation of the four exocyclic PdCl2 units from [(PdCl2)(4)LM] occurs in pyridine, but the compounds are stable in N,N-dimethylformamide (DMF) or dimethylsulfoxide (DMSO) and can be stepwise reduced via two one-electron reversible or quasi-reversible processes, prior to an irreversible electroreduction of the bound PdCl2 group at more negative potentials. This metal-centered reduction leads to a [LM](2-) product which is then further reduced to [LM](3-) and [LM](4-) at the electrode surface. The first two reductions of the heteropentametallic compounds are easier than those of the monometallic [LM] species but generally more difficult than reduction of the related octacationic [L'M](8+) derivatives (L' = the octamethylated free-base dianion) whose redox properties were previously reported. The Cd-II octacation [L'Cd](8+), isolated as an iodide salt, was also synthesized for the first time in the current study, and its spectroscopic and electrochemical properties are compared to that of the previously examined analogues.