4,6-bis[[N-methyl-N'-(pyridin-2-yl)methylidene]hydrazino]-2-phenylpyrimidine | 864368-84-3

• 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: 4,6-bis[[N-methyl-N'-(pyridin-2-yl)methylidene]hydrazino]-2-phenylpyrimidine
• 英文别名: pyridine-2-carboxaldehyde[2-phenyl-pyrimidine-4,6-diyl]bis(methylhydrazone)；pyridine-2-carboxaldehyde[2-phenylpyrimidine-4,6-diyl]bis(methylhydrazone)
• CAS: 864368-84-3
• 化学式: C₂₄H₂₂N₈
• 分子量: 422.492
• InChiKey: QDHHKWFAGVJZTQ-LGLLBGERSA-N

物化性质

• 沸点：
  572.8±60.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.87
• 重原子数：
  32.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  82.76
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  4,6-bis[[N-methyl-N'-(pyridin-2-yl)methylidene]hydrazino]-2-phenylpyrimidine 、 mercuric triflate 以 氘代乙腈 为溶剂， 生成 [Hg4(pyridine-2-carboxaldehyde[2-phenyl-pyrimidine-4,6-diyl]bis(methylhydrazone))4](CF3SO3)8
  参考文献：
  名称：

  大型重金属阳离子（Hg2 + 和 Pb2 +）与双三齿配体的配位结构：溶液和固态研究

  摘要：

  通过双（甲基肼基）苯基嘧啶和双（肼基）苯基嘧啶分别与吡啶-2-甲醛缩合获得的同源双三齿配体 1 和 2H2 对 Hg2 + 和 Pb2 + 络合的溶液和固态研究有为网格和机架物种的形成提供了证据。对于 Hg2 +，除了网格种类之外，几乎没有迹象表明网格复合物 [Hg4 (2H2) 4] (CF3SO3) 8 具有晶体学特征。对于 Pb2+，唯一容易分离的结晶物质是配体 1 和 2H2 的架复合物。

  DOI：

  10.1002/zaac.200700354
• 作为产物：
  描述：

  4,6-二羟基-2-苯基嘧啶 在 三氯氧磷 作用下， 以 乙醇 为溶剂， 反应 14.0h， 生成 4,6-bis[[N-methyl-N'-(pyridin-2-yl)methylidene]hydrazino]-2-phenylpyrimidine
  参考文献：
  名称：

  Electronic absorption and emission properties of bishydrazone [2 × 2] metallosupramolecular grid-type architectures

  摘要：

  Several ditopic ligands containing two tridentate bishydrazone coordination subunits and their Zn(II) and Cd(II) [2 x 2] grid-type complexes were prepared and their photoluminescent properties studied. A special attention was devoted to the influence of the orientation of the hydrazone group N-N=in the core of the ligands and their complexes. Its reversal from [pyridine=N-N-pyrimidine] (L1) to [pyridinee-N-N=pyrimidine] (L2) has a strong impact on the observed absorption and emission behaviour of particular ligands (L1 and L2) as well as of their [2 x 2] grid assemblies. The further lateral functionalization of the ligands led to different emission quantum yields of the resulting grids, while their emission and absorption spectra varied very little. The simplest derivative L1 turned out to have the best performance with, for its Zn(II) complex, relatively high quantum yield 60%.

  DOI：

  10.1016/j.ica.2019.05.017

文献信息

• Self‐Assembly, Structure and Solution Dynamics of Tetranuclear Zn ²⁺ Hydrazone [2×2] Grid‐Type Complexes
  作者：Mihail Barboiu、Mario Ruben、Georges Blasen、Nathalie Kyritsakas、Elizabeth Chacko、Manisha Dutta、Olga Radekovich、Kimberly Lenton、David J. R. Brook、Jean‐Marie Lehn

  DOI：10.1002/ejic.200500963

  日期：2006.2

  π–π stacking between the phenyl ring and the hydrazone units of the perpendicular ligands in the complexes induces a perfect orthogonal arrangement suitable for applications in self-organized metallosupramolecular systems. Zinc complexes provide an opportunity to study the acid–base chemistry without the added effects due to paramagnetism or redox chemistry. The intermediate protonated grids undergo

  我们描述了基于双（腙）嘧啶络合亚基和八面体配位的 [2×2]Zn2+4 网格络合物的自组装过程以及结构和物理化学性质，其中涉及双三齿配体 7-12 Zn2+ 离子。NMR 光谱数据和 X 射线晶体结构结果表明，在溶液和固态中，配合物 13-18 采用非常紧凑的排列，提供稳定的 [2×2] 腙网格阵列。苯环和配合物中垂直配体的腙单元之间的 π-π 堆积诱导了完美的正交排列，适用于自组织金属超分子系统中的应用。锌配合物提供了研究酸碱化学的机会，而不会因顺磁性或氧化还原化学而产生额外影响。中间质子化网格在 NMR 时间尺度上经历相对快速的质子交换，尖锐的嘧啶质子共振的存在表明负电荷沿配体骨架存在显着离域。观察到苯环的旋转。它可能涉及一种机制，其中一个配体部分解离，允许最初插入的苯基在末端吡啶重新配位之前旋转。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
• Hg^IIGrid-Like Metallo-Supramolecular Coordination Architecture presenting Acetonitrile-π and Anion-π Interactions with the Pyrimidine Ring
  作者：Juan Ramírez、Adrian-Mihail Stadler

  DOI：10.1002/zaac.200900077

  日期：2009.7

  distance between the nitrogen atom of a molecule of acetonitrile and the centroid of the closest pyrimidine ring, and the distance between the oxygen atom of a triflate and the centroid of the closest pyrimidine ring are of about 3 A, thus suggesting acetonitrile-π, respectively triflate-π interactions.

  测定了通过双（甲基肼基）苯基嘧啶与吡啶-2-甲醛缩合获得的双三齿配体 1 的 HgII 网格状复合物 [Hg414](CF3SO3)8 的固态 X 射线晶体结构。它证实了先前基于 1D 和 2D NMR 研究确定的结构。发现作为网格形成结果的配体延伸幅度约为 15 A。乙腈分子的氮原子与最近的嘧啶环的质心之间的距离，以及之间的距离三氟甲磺酸酯的氧原子和最近的嘧啶环的质心约为 3 A，因此分别表明乙腈-π 和三氟甲磺酸酯-π 相互作用。
• Protonic modulation of redox properties in ionisable [2 × 2] grid-like metalloarrays
  作者：Lindsay H. Uppadine、Jean-Paul Gisselbrecht、Jean-Marie Lehn

  DOI：10.1039/b315352e

  日期：——

  The oxidation state of the cobalt centres can be controlled by modification of the protonation state in [2 × 2] grid-like arrays based on ionisable bis(hydrazone) ligands, allowing conversion of the paramagnetic CoII4 into the diamagnetic CoIII4 grid.

  钴中心的氧化态可以通过改变基于可电离双腙配体的 [2 × 2] 网格状阵列中的质子态来控制，从而使顺磁性 CoII4 转变为二磁性 CoIII4 网格。
• Grid–double-helicate interconversion
  作者：Adrian-Mihail Stadler、Christophe Burg、Juan Ramírez、Jean-Marie Lehn

  DOI：10.1039/c3cc38580a

  日期：——

  An interconversion between a binuclear CuI double helicate and a tetranuclear CuII grid is reported. The passage from the CuI double helicate to the CuII grid occurs through oxidation of CuI into CuII or through displacement of CuI by CuII. The conversion of the CuII grid into the CuI double helicate occurs through treatment of the grid with triflic acid, reduction of CuII with ascorbic acid, and neutralization with triethylamine. During the studies, in order to ascertain the structure of CuI complexes, a heteroleptic binuclear CuI double helicate was generated.

  报告了双核 CuI 双螺旋与四核 CuII 网格之间的相互转化。从 CuI 双螺旋到 CuII 栅格的转换是通过 CuI 氧化成 CuII 或 CuI 被 CuII 置换实现的。CuII 网格向 CuI 双螺旋的转化是通过用三氟甲酸处理网格、用抗坏血酸还原 CuII 以及用三乙胺中和实现的。在研究过程中，为了确定 CuI 复合物的结构，生成了一种异极双核 CuI 双螺旋。