methyl viologen radical cation chloride | 79028-21-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: methyl viologen radical cation chloride
• 英文别名: methylviologen cation-radical；monocation radical of methylviologen；N,N'-Dimethyl-4,4'-bipyridinium chloride；1,1'-dimethyl-monohydro-[4,4']bipyridyliumyl; chloride
• CAS: 79028-21-0
• 化学式: C₁₂H₁₄N₂*Cl
• 分子量: 221.71
• InChiKey: YUJFFVJDJTVLGK-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.59
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  7.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl viologen radical cation chloride 在 氯化胆碱 、 尿素 作用下， 生成 paraquat dichloride
  参考文献：
  名称：

  刺激介导的超稳定自由基形成

  摘要：

  有机自由基通常是通过添加化学试剂或光化学方法而形成的反应性且通常为短寿命的物种。由于其开壳式电子结构，基于其磁性能和理想的光谱行为，它们引起了人们的关注。氧化还原敏感分子，如紫精（V），经过单电子还原形成自由基。这些物质在多种应用中具有巨大的潜力，但由于它们被空气中的氧气迅速淬灭而受到限制。以甲基紫精（MV）为例，我们显示了MV自由基（MV + ⋅）可通过电化学，化学和光化学刺激以及新型的热刺激在各种深共熔溶剂（DES）中形成，并且被发现异常稳定。DES的导电特性允许通过一种简单，经济的方法来制造好氧电致变色器件。我们的报告代表了一种独特的方法，可以在不改变母体结构的情况下延长空气中的反应性自由基寿命。

  DOI：

  10.1016/j.chempr.2020.05.005
• 作为产物：
  描述：

  paraquat dichloride 在 叔丁醇 作用下， 以 水 为溶剂， 生成 methyl viologen radical cation chloride
  参考文献：
  名称：

  水溶液中甲基紫精的脉冲辐解

  摘要：

  在各种pH下对无空气的甲基紫精水溶液（MV 2+）进行脉冲辐解。e – aq对MV 2+的侵蚀，其中k（e – aq + MV 2 +）= 7.5×10 10 dm 3 mol –1 s –1，导致长寿命自由基阳离子（MV˙ +），其在392.5纳米具有两个最大吸收（Iμ 392.5 =4200米2摩尔-1）和600纳米（Iμ 600 =1450米2摩尔-1）。H原子与pH 1的MV 2+反应形成两个物种，它们具有叠加的吸收带。通过计算机模拟，将它们分解为以下吸收：（1）质子化形式的自由基阳离子（MV˙+ H +），其乘以k（H + MV 2 +）=（3.5±0.2） ）×10 8分米3摩尔-1小号-1，有2个吸收最大值在390nm（Iμ 390 =1700米2摩尔-1）和595纳米（Iμ 595 =760米2摩尔-1）并通过二阶动力学衰减，其中k = 3.5×10 9 dm 3 mol –1

  DOI：

  10.1039/f19827802467

文献信息

• Titanium dioxide and cadmium sulfide colloids stabilized by .beta.-cyclodextrins: tailored semiconductor-receptor systems as a means to control interfacial electron-transfer processes
  作者：Itamar Willner、Yoav Eichen

  DOI：10.1021/ja00256a056

  日期：1987.10

  directed in recent years toward the preparation of semiconductor particles in colloidal forms to improve their light harvesting and interfacial electron-transfer properties. Stabilization of semiconductor colloids by polymers, microemulsions, and vesicle encapsulation has been reported. Here they report on a novel method for stabilizing semiconductor colloids by ..beta..-cyclodextrin (..beta..-CD).

  半导体颗粒的光催化活性在合成以及太阳能转换和储存的手段中具有重要意义。半导体-溶液界面处的电荷喷射或电荷注入等电子转移反应是控制半导体光催化活性的重要因素。溶质对半导体表面的静电吸引改善了从受激半导体到溶质继电器的电荷喷射。染料对半导体表面的吸附，即通过疏水相互作用，导致向半导体有效注入电荷，因此在紫外区工作的半导体的光催化活性可以转移到可见光吸收光谱。近年来，大量努力还致力于制备胶体形式的半导体颗粒，以改善它们的光收集和界面电子转移特性。已经报道了通过聚合物、微乳液和囊泡封装来稳定半导体胶体。在这里，他们报告了一种通过 ..beta..-环糊精 (..beta..-CD) 稳定半导体胶体的新方法。
• Photosensitized Reduction of Methylviologen through the Energy Transfer from Triplet Dyes to 9-Anthracenecarboxylate Anion
  作者：Yoshiharu Usui、Yoshimi Sasaki、Yukie Ishii、Katsumi Tokumaru

  DOI：10.1246/bcsj.61.3335

  日期：1988.9

  The reaction mechanism for photosensitized reduction of methylviologen, MV2+ through the triplet–triplet energy transfer from organic dyes to 9-anthracenecarboxylate, AC− was investigated. From the kinetic analysis on MV\underset.+ formation, it was estimated that both efficiencies of the energy transfer and of the electron transfer from 3AC− to MV2+ were close to unity.

  研究了通过从有机染料到 9-蒽羧酸盐 AC− 的三线态-三线态能量转移来光敏还原甲基紫精 MV2+ 的反应机制。从对 MV\underset.+ 形成的动力学分析，估计能量转移和从 3AC- 到 MV2+ 的电子转移效率接近统一。
• Photoinduced Reduction of Methylviologen by Ascorbate Using Chlorophyllin in Liposome System
  作者：Seiji Hidaka、Eizo Matsumoto、Fujio Toda

  DOI：10.1246/bcsj.58.207

  日期：1985.1

  Photoindeced electron transport across bilayer lipid membrane was studied, using chlorophyllin (Chln), a water-soluble derivative of chlorophyll. Photoreduction of methylviologen (MV2+) by ascorbate was observed only in the liposome system containing ascorbate in the internal aqueous phase and MV2+ in the external aqueous phase. This suggests asymmetry of bilayer lipid membrane. This reaction rate was not affected by the addition of carbonyl cyanide m-chlorophenylhydrazone in the system buffered by tris(hydroxymethyl)aminomethane (Tris), but strongly affected by N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid. In the system buffered by Tris, a proton carrier is not Chin having carboxyl groups but Tris possessing primary amine group. Replacement of the central Mg of Chin with Zn gives a higher rate of MV2+ photoreduction, but when Cu was used in place of Zn, photoreduction was not observed. The central metal may affect the redox potential and the life time of excited Chln.

  利用叶绿素（Chln）这种叶绿素的水溶性衍生物，研究了双层脂膜上的光诱导电子传递。只有在内部水相中含有抗坏血酸，外部水相中含有 MV2+ 的脂质体系统中，才能观察到抗坏血酸对甲基维罗庚（MV2+）的光还原作用。这表明双层脂膜不对称。在由三羟甲基氨基甲烷（Tris）缓冲的体系中，加入间氯苯基腙羰基反应速率不受影响，但加入 N-2-羟乙基哌嗪-N′-2-乙磺酸则影响很大。在由 Tris 缓冲的体系中，质子载体不是具有羧基的 Chin，而是具有伯胺基团的 Tris。用锌代替钦的中心镁可提高 MV2+ 的光反应速率，但用铜代替锌时，则观察不到光反应。中心金属可能会影响氧化还原电位和激发 Chln 的寿命。
• Electron-transfer reactions of a photosensitized water-soluble zinc porphyrin
  作者：Dominique Le Roux、Jean-Claude Mialocq、Oleg Anitoff、G�rard Folcher

  DOI：10.1039/f29848000909

  日期：——

  The photoreactivity of the water-soluble zinc derivative of 5,10,15,20-tetra(N-methyl-pyridinium-3-yl)porphyrin [Zn(MePy)4P4+] has been investigated using the laser-photolysis technique and shown to be the same as that of the pyridinium-4-yl isomer. Electron transfer from the triplet state of this porphyrin to methyl viologen is greatly influenced by coulombic effects. In the presence of chloride ions

  使用激光光解技术研究了5,10,15,20-四（N-甲基-吡啶-3-基）卟啉[Zn（MePy）4 P 4+ ]的水溶性锌衍生物的光反应性并显示与吡啶基-4-基异构体相同。从该卟啉的三重态到甲基紫精的电子转移受到库仑效应的极大影响。在存在氯离子的情况下，（MV 2 + ·Cl –）离子对的存在可以解释所观察到的直接电子转移的动力学。铜离子淬灭三重态，二级速率常数k T + Cu 2+ =（1.5 + 0.1）×10 6 dm 3 mol–1 s –1与使用甲基紫精观察到的相似。但是，没有发现光氧化还原过程的迹象。
• Radiolytic reductions and oxidations in dimethyl sulfoxide solutions: solvent effects on reactivity of halogen atom complexes
  作者：M. Kumar、P. Neta

  DOI：10.1021/j100187a032

  日期：1992.4

  Radiolysis of dimethyl sulfoxide (DMSO) solutions containing various additives was used to achieve clean one-electron reduction of oxidation of solutes. Pulse radiolysis of benzoquinone in DMSO solutions containing acetone and triethylamine permitted conversion of all primary radicals into reducing species. The total yield of reduction in the gamma-radiolysis of methyl viologen solutions was found to be 0.37-mu-mol/J. In the pulse radiolysis of TMPD and triphenylamine in aerated DMSO containing LiCl and/or CCl4, all the primary radicals were converted into oxidizing species and gave a maximum yield of 0.39-mu-mol/J. In the latter systems, oxidation was partly by halogen atom complexes. The reactivity of complexes of DMSO (DMSO.Cl, DMSO.Br) and of halide ions (Br2.-,I2.-) was examined for several organic compounds. DMSO.Cl oxidizes chlorpromazine, triphenylamine, and zinc porphyrin with rate constants of the order of 10(7)-10(8) M-1 s-1, and the rates increase upon addition of CH2Cl2 as well as upon addition of water and formamide. DMSO.Cl also reacts with olefins by addition of Cl to the double bond; the rate constants increase upon increasing the electron-donating properties of the substituents on the double bond. The rate constants for oxidation of chlorpromazine by Br2.- and I2.- increase by more than 2 orders of magnitude upon changing the solvent from DMSO gradually to water. The change was less with acetonitrile/water mixtures, and the difference is probably due to differences in ion solvation.