[Me2qpy](PF6)2 | 125330-13-4

• 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: [Me2qpy](PF6)2
• 英文别名: N'',N'''-dimethyl-2,2':4,4'':4',4'''-quaterpyridinium hexafluorophosphate；N'',N'''-dimethyl-2,2':4,4'':4',4'''-quaterpyridinum hexafluorophosphate；[Me₂qpy](PF6)2；[Me2Qpy(2+)][PF6]2
• CAS: 125330-13-4
• 化学式: C₂₂H₂₀N₄*2F₆P
• 分子量: 630.356
• InChiKey: SARUHOKFHQASRX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.51
• 重原子数：
  33.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  33.54
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  [Me2qpy](PF6)2 在 四丁基氯化铵 作用下， 以 丙酮 为溶剂， 以398 mg的产率得到N'',N'''-dimethyl-4,4':2',2'':4'',4'''-quaterpyridinium chloride
  参考文献：
  名称：

  Syntheses and properties of complexes with bis(2,2′-bipyridyl)ruthenium(II) moieties coordinated to 4,4′:2′,2′′:4′′,4′′′-quaterpyridinium ligands

  摘要：

  Eleven new complexes of the form cis-[Ru-II(bpy)(2)(L-A)](4+) (bpy = 2,2'-bipyridyl; L-A = a pyridinium-substituted bpy derivative) have been prepared and isolated as their PF6- salts. Characterisation involved various techniques including H-1 NMR spectroscopy and MALDI mass spectrometry. The UV-Vis spectra show intense intraligand pi -> pi* absorptions and metal-to-ligand charge-transfer (MLCT) bands with two distinct maxima in the visible region. Small shifts in the MLCT bands correlate with the electron-withdrawing strength of the ligand L-A. Cyclic voltammograms show quasi-reversible or reversible Ru-III/II oxidation waves, and two or more ligand-based reductions with varying degrees of reversibility. The variations in the redox potentials correlate with changes in the structure of L-A, and also with the MLCT energies. Differential pulse voltammetry allows the first reduction process for two of the complex salts to be resolved into two peaks. Single-crystal X-ray structures have been solved for three of the new complex salts and also for a pro-ligand salt. Two carboxylate-functionalised compounds have been tested as photosensitizers on TiO2-coated electrodes, but show only negligible efficiencies, in accord with expectations. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2011.04.018
• 作为产物：
  描述：

  4,4'-联吡啶 在 palladium on activated charcoal 作用下， 以 水 、 丙酮 为溶剂， 反应 78.5h， 生成 [Me2qpy](PF6)2
  参考文献：
  名称：

  2,2':4,4'':4',4'''-quaterpyridyl: a building block for the preparation of novel redox reagents. 1. Preparation and quaternization

  摘要：

  DOI：

  10.1021/jo00294a007

文献信息

• Light-driven biocatalytic reduction of α,β-unsaturated compounds by ene reductases employing transition metal complexes as photosensitizers
  作者：Martyn K. Peers、Helen S. Toogood、Derren J. Heyes、David Mansell、Benjamin J. Coe、Nigel S. Scrutton

  DOI：10.1039/c5cy01642h

  日期：——

  Efficient and cost effective nicotinamide cofactor regeneration is essential for industrial-scale bio-hydrogenations employing flavin-containing biocatalysts such as the Old Yellow Enzymes.

  在工业规模生物氢化过程中，使用含有黄素辅酶的生物催化剂（如旧黄酶）时，高效且成本效益高的烟酰胺辅因子再生至关重要。

• Syntheses and Properties of Two-Dimensional Charged Nonlinear Optical Chromophores Incorporating Redox-Switchable <i>cis</i>-Tetraammineruthenium(II) Centers
  作者：Benjamin J. Coe、James A. Harris、Lathe A. Jones、Bruce S. Brunschwig、Kai Song、Koen Clays、Javier Garín、Jesús Orduna、Simon J. Coles、Michael B. Hursthouse

  DOI：10.1021/ja0424124

  日期：2005.4.1

  ligands or related chelates based on 2,2':4,4":4',4'''-quaterpyridyl and have been characterized by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses beta have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible

  在这篇文章中，我们描述了一系列新的络盐，其中给电子的顺式-Ru(II)(NH3)(4)}(2+) 中心连接到两个接受电子的 N-甲基/芳基-吡啶鎓组。这些 V 形复合物包含单齿 4,4'-联吡啶衍生配体或基于 2,2':4,4":4',4'''-四吡啶基的相关螯合物，并已通过使用各种技术进行表征，包括电子吸收光谱和循环伏安法。分子二次非线性光学 (NLO) 响应β 已通过使用 800 nm 的超瑞利散射以及通过斯塔克（电吸收）光谱研究对强烈的可见 d --> pi 金属-to 确定-配体电荷转移带。这些实验表明，这些偶极伪 C(2v) 生色团表现出 β 张量的两个重要组成部分，即 beta(zzz) 和 beta(zyy)，它们之间的差异对于非螯合系统最为显着。时间相关的密度泛函理论和有限场计算有助于进一步阐明新发色盐的电子结构和相关的线性和 NLO 特性。
• Three-Dimensional Nonlinear Optical Chromophores Based on Metal-to-Ligand Charge-Transfer from Ruthenium(II) or Iron(II) Centers
  作者：Benjamin J. Coe、James A. Harris、Bruce S. Brunschwig、Inge Asselberghs、Koen Clays、Javier Garín、Jesús Orduna

  DOI：10.1021/ja053879x

  日期：2005.9.28

  this article, we describe a series of new complex salts in which electron-rich transition-metal centers are coordinated to three electron-accepting N-methyl/aryl-2,2':4,4' ':4',4' ''-quaterpyridinium ligands. These complexes contain either Ru(II) or Fe(II) ions and have been characterized by using various techniques, including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic

  在本文中，我们描述了一系列新的络盐，其中富电子过渡金属中心与三个接受电子的 N-甲基/芳基-2,2':4,4' ':4',4' 配位''-季吡啶鎓配体。这些配合物含有 Ru(II) 或 Fe(II) 离子，并已使用各种技术进行表征，包括电子吸收光谱法和循环伏安法。分子二次非线性光学 (NLO) 响应 beta 已通过使用 800 nm 的超瑞利散射以及通过斯塔克（电吸收）光谱研究对强烈的可见 d --> pi* 金属-配体电荷转移带进行测定. 后面的实验表明，这些假定的八极 D(3) 生色团表现出β张量的两个重要组成部分，这些组成部分与向偶极激发态的过渡相关。涉及时间相关密度泛函理论和有限场法的计算有助于进一步阐明新发色盐的电子结构和相关的线性和 NLO 特性。
• Syntheses and electronic and optical properties of complexes of the bis(2,2′-bipyrazyl)ruthenium unit
  作者：Benjamin J. Coe、Martyn K. Peers、Nigel S. Scrutton

  DOI：10.1016/j.poly.2015.04.028

  日期：2015.8

  Seven new complexes of the form cis-[Ru-II(bpz)2(L-L)(n+) (bpz = 2,2'-bipyrazyl: n = 2; L L = 4,4'-bis (tert-butyl)-2,2'-bipyridyl, 4,4'-dipheny1-2,2'-bipyridyl, 4,4'-dichloro-2,2'-bipyridyl, 4,4'-diamino-2, 2'-bipyridyl, 4,4'-bis(trifluoromethyl)-2,2'-bipyridyl, 4,4'-bis(methoxycarbonyl)-2,2'-bipyridyl: n = 4; L-L = N '',N'"-dimethy1-4,4':2',2 '':4 '',4'''-quaterpyridinium) are prepared and isolated as their PF6- and Cl- salts. Improved methods for synthesising bpz and 4,4'-bis(trifluoromethyl)-2,2'-bipyridyl are described also. Characterisation involves various techniques including H-1 NMR spectroscopy and mass spectrometry. The new compounds are studied alongside the known species where n = 2 and L-L = 2,2'-bipyridyl, 4,4'-dimethy1-2,2'-bipyridyl or 2,2'-bipyrimidine. Their UV-Vis spectra display intense intraligand pi -> pi* absorptions, and also metal-to-ligand charge-transfer (MLCT) bands with two resolved maxima in the visible region. Red-shifts in the MLCT bands occur as the electron-donating strength of L L increases. Cyclic voltammograms show reversible Ru-III/II oxidation waves, and several ligand-based reductions that are also mostly reversible. The variations in the redox potentials correlate with changes in the MLCT energies. Time-dependent density functional theory calculations give relatively good correlations with the experimental UV Vis spectra for selected complexes when using the MOB functional and basis sets Def2-QZVP (on Ru) and Def2-SVP (on all other atoms) in acetonitrile. The lowest energy visible absorption band is confirmed to be due to Ru-II -> bpz MLCT, while further such transitions occur along with MLCT to L L at higher energies. (C) 2015 The Authors. Published by Elsevier Ltd.