4,4'-(CH3(OCH2CH2)7OCO)2-2,2'-bipyridine

• 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: 4,4'-(CH3(OCH2CH2)7OCO)2-2,2'-bipyridine
• 英文别名: 2-[2-[2-[2-[2-[2-(2-Methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-[4-[2-[2-[2-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxycarbonyl]pyridin-2-yl]pyridine-4-carboxylate；2-[2-[2-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-[4-[2-[2-[2-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxycarbonyl]pyridin-2-yl]pyridine-4-carboxylate
• 化学式: C₄₂H₆₈N₂O₁₈
• 分子量: 889.005
• InChiKey: PYJIILDFXJQRDW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  62
• 可旋转键数：
  47
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  208
• 氢给体数：
  0
• 氢受体数：
  20

反应信息

• 作为反应物：
  描述：

  cobalt(II) perchlorate 、 4,4'-(CH3(OCH2CH2)7OCO)2-2,2'-bipyridine 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  杂化氧化还原聚醚熔体中的电子和质量传输：Co 和 Fe 联吡啶与聚醚链相连

  摘要：

  电子自交换反应与物理扩散的耦合已被用于测量一系列未稀释的金属络合物熔盐 [M(bpy(CO2MePEG)2)3](ClO4)2 中的电子转移速率常数，其中 M = Co(II/ I) 和 Fe(III/II) 和 MePEG 是 MW 150、350 和 550 的低聚聚醚。熔体中的物理自扩散速率随连接的聚醚链长度变化超过 103 倍，而电子转移速率常数显示没有强烈的系统依赖性。电子转移速率和活化参数表明，金属络合物核在其附着的聚醚“溶剂”壳内相对于电子转移速率快速移动，电子转移速率接近绝热，活化势垒大，反映附着的聚醚链明显无法起作用作为一种自由流动的“溶剂”。测量熔体的离子电导率以检查存在较小程度的离子和电子迁移效应。扩散和异质...

  DOI：

  10.1021/ja962531m

文献信息

• Electrocatalysis in Nucleic Acid Molten Salts
  作者：Anthony M. Leone、Dominic O. Hull、Wei Wang、H. Holden Thorp、Royce W. Murray

  DOI：10.1021/jp048995l

  日期：2004.11.1

  This paper describes redox chemistry in semisolid molten salts ionic liquids of DNA in which the counterions of the phosphates are redox-active metal complexes with bipyridine ligands labeled with MW 350 poly(ethylene glycol) (PEG) "tails", e.g., M(bpY(350))(3)DNA (where M = Co, Ni, and bpy(350) = 4,4'-(CH3(OCH2-CH2)(7)OCO)(2)-2,2'-bipyridine). Other redox-active metal complexes are added to the M(bpy(350))(3)DNA melt: (a) the PEG-tailed metal bipyridine complexes Fe(bpy(350))(3)(ClO4)(2) and Ru(bpy(350))(3)(ClO4)(2) and (b) the nontailed complexes Os(bpy)(3)CI2 (bpy = 2,2'-bipyridine) and Os(bpy)(2)dppzCl(2) (dppz = dipyridophenazine). In example a, electrogeneration of the powerful oxidizers [Fe(bpy(350))(3)](3+) and [Ru(bpy(350))(3)](3+) gives microelectrode voltammetry indicative of electrocatalytic oxidation of DNA base sites. Since physical diffusion of the metal complexes is slow in the viscous semisolids (and that of DNA is nil), the rate of electron hopping between the base sites of the DNA becomes a significant contributor to the overall charge transport rate, as deduced from analysis of the voltammetry. DNA base site self-exchange rate constants of 1.1 x 10(6) and 1.8 x 10(6) s(-1) are estimated from measurements using Fe(bpy(350))(3)(3+) and Ru(bpy(350))(3)(3+) oxidants, respectively. In example b, a complex known to be a DNA intercalator in aqueous solutions is found to not be an intercalator in the DNA molten salt environment, as deduced from measurements showing the physical diffusion coefficients of aqueous nonintercalator Os(bpy)(3)Cl-2 and aqueous intercalator Os(bpy)(2)dppzCl(2) to be indistinguishable in the M(bpy(350))(3)DNA melt.
• Room-Temperature Molten Salts of Ruthenium Tris(bipyridine)
  作者：Hitoshi Masui、Royce W. Murray

  DOI：10.1021/ic9706111

  日期：1997.10.1

  Attaching poly(ethylene glycol)-mono(methyl ether) (MW 350) chains to [Ru(bpy)(3)](2+) complexes via 4,4'-bipyridine ester linkages produces room temperature, highly viscous, molten salt forms of this well-known complex. This paper describes the synthesis and properties of a series of such complexes bearing two, four, or six polyether chains. Differential scanning calorimetry, rheometry, microelectrode voltammetry, and ac impedance spectroscopy were used to determine the dependence of physical and transport properties of the Ru complex melts on the number of polyether tails. The coupling of electron hopping and physical diffusion in voltammetrically generated mixed-valent layers is analyzed using the Dahms-Ruff relationship, yielding self-exchange rate constants, k(ex), for the Ru(III/II) and Ru(II/I) couples. An activation analysis shows that these reactions are adiabatic, or nearly so, and the slowing of their rates relative to that of the parent [RU(bpy)(3)](2+) complex in fluid solutions is caused by large thermal barriers.
• Solid State Electrochemically Generated Luminescence Based on Serial Frozen Concentration Gradients of Ru^III/II and Ru^II/I Couples in a Molten Ruthenium 2,2‘-Bipyridine Complex
  作者：Karolyn M. Maness、Hitoshi Masui、R. Mark Wightman、Royce W. Murray

  DOI：10.1021/ja9636754

  日期：1997.4.1

  The attachment of two polyethylene glycol tails (n = 7, MW = 350) to ruthenium tris(bipyridine) via ester links on the 4,4'-positions of one of the bipyridine ligands yields a highly viscous (eta approximate to 10(7) cP) molten salt (abbreviated [Ru(bpy)(2)(bpy(CO(2)MePEG350)(2))](ClO4)(2)) that glasses at ca. -5 degrees C. At room temperature, the ionic conductivity of the melt is sufficiently high that application of 2.4 V across the fingers of a Pt interdigitated electrode array (IDA) coated with the melt leads to the electrolytic development of serial concentration gradient microstructures of Ru-III/II and Ru-II/I states. At the intersection of the two concentration gradients, in the interior of the coating, reaction between the Ru-III and Ru-I states leads to ECL emission with an efficiency of 0.2% photons/electron. Cooling a concentration gradient-containing film to -20 degrees C under voltage bias, so as to preserve the gradient microstructure, yields a film that has an emission efficiency of 0.1%, a current and light emission response that rapidly changes with the applied voltage bias, and a diode-like current-voltage profile with a ca. 100 rectification ratio.
• Emmenegger, Franzpeter; Williams, Mary Elizabeth; Murray, Royce W., Inorganic Chemistry, <hi>1997</hi>, vol. 36, # 14, p. 3146 - 3151
  作者：Emmenegger, Franzpeter、Williams, Mary Elizabeth、Murray, Royce W.

  DOI：——

  日期：——
• Transport and Electron Transfer Dynamics in a Polyether-Tailed Cobalt Bipyridine Molten Salt:  Electrolyte Effects
  作者：Mary Elizabeth Williams、Leslie J. Lyons、Jeffrey W. Long、Royce W. Murray

  DOI：10.1021/jp971519t

  日期：1997.9.1

  Transport, ionic conductivity, and viscosity properties of the metal complex molten salt [Co(bpy(CO(2)MePEG-350)(2))(3)](ClO4)(2) (MePEG = monomethyl-terminated polyether, average MW = 350) are strongly affected by dissolution of LiClO4 electrolyte in the melt. The physical self-diffusion of the [Co(bpy(CO(2)MePEG-350)(2))(3)](2+) and the rate of [Co(bpy(CO(2)MePEG-350)(2))(3)](2+/+) electron self-exchange are slowed, the melt Viscosity increased and ionic conductivity decreased, and thermal activation barriers for all are enhanced by increasing [LiClO4]. Most of the effects are associated with the Li+ cation/polyether coordination well-known in polymer electrolytes, in which chain cross-linking and a decrease in chain segmental mobility occurs. The [Co(bpy(CO(2)MePEG-350)2)(3)](2+/+) electron self-exchange reaction is shown to be adiabatic (kinetic prefactor cn. 10(13) s(-1)), and modest changes in its rate with [LiClO4] are caused by changes in the electron transfer barrier energy. The results ate used to draw a hierarchy of dynamics in the metal complex melt in which, for [LiClO4] = 1.3 M, the average diffusive jump rate is ca. 3 s(-1), the average electron hopping rate is ca. 2 x 10(4) s(-1), and the rate of short-range motions of the hard metal complex core within its soft polyether shell (producing adjacent core-core contacts) is ca. greater than or equal to 10(5) s(-1).