6,6'-bis(4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl 2-yl)-2,2'-bipyridine | 155379-19-4

• 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: 6,6'-bis(4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl 2-yl)-2,2'-bipyridine
• 英文别名: 6,6'-bis(3''-oxide-1''-oxyl-4'',4'',5'',5''-tetramethylimidazoline-2''-yl)-2,2'-bipyridine
• CAS: 155379-19-4
• 化学式: C₂₄H₃₀N₆O₄
• 分子量: 466.54
• InChiKey: TYUSXQVEQSUFCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.09
• 重原子数：
  34.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  124.2
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  zinc perchlorate 、 6,6'-bis(4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl 2-yl)-2,2'-bipyridine 以 二氯甲烷 、 乙酸乙酯 为溶剂， 以95%的产率得到[Zn(6,6'-bis(3''-oxide-1''-oxyl-4'',4'',5'',5''-tetramethylimidazoline-2''-yl)-2,2'-bipyridine)](ClO4)2, CH3CN
  参考文献：
  名称：

  Nitronyl Nitroxide Biradicals as Tetradentate Chelates:  Unusually Large Metal−Nitroxide Ferromagnetic Interactions

  摘要：

  A series of mononuclear transition metal complexes of the tetradentate (N2O2) 6,6'-bis(3 "-oxide-1 "-oxyl-4 ",4 ",5 ",5 "-tetramethylimidazoline-2 "-yl)-2,2'-bipyridine (NIT-bpy) has been prepared and characterized by spectroscopic, magnetic, and single-crystal X-ray diffraction studies. The free NIT-bpy ligand is planar with an anti-conformation, whereas in each complex this ligand is tetracoordinated to the metal in a syn-conformation comprising the equatorial plane of a distorted octahedron. Complexes differ by the nature or the ancillary ligands occupying the trans-axial positions, these being two water molecules in [Ni-II(NIT-bpy). 2H(2)O](ClO4)(2), 1, one molecule of water and one perchlorate anion in [M(NIT-bpy). H2O . ClO4]ClO4 (M = Ni(II), 2; Mn(II), 3; Co(II), 4), or two perchlorate anions in [Cu-II(NIT-bpy). 2ClO(4)], 5. The ferromagnetic metal-nitroxide coupling found for the nickel complex 1 (J(12) = + 39.6 cm(-1)) arises from near-coplanarity between the pi-conjugated radical plane and the equatorial plane of the trans-diaqua{Ni(N-2O2)(H2O)(2)} octahedron. Deviations from this geometry lead to antiferromagnetic components that are dominant in complex 1 (J(23) = - 48.7 cm(-1)) and tend to reduce the extent of the ferromagnetic interactions in complex 2 (J(12) = +27.8 cm(-1) and J(23) = +6.9 cm(-1)). For the Mn2+ complex 3, variable temperature studies indicate antiferromagnetic behavior J = - 65.3 cm(-1), but with weak intermolecular ferromagnetic interactions zJ' = + 0.22 cm(-1). For the Co2+ complex 4. experimental data were best explained as a weak ferromagnetic interaction J(12) = + 0.40 cm(-1) and a relatively strong antiferromagnetic interaction J(23) = - 28.0 cm(-1). The Cu2+ complex 5 exhibits strong antiferromagnetic behavior J = -166.8 cm(-1). The magnetic data of the [M'(NIT-bpy)](ClO4)(2) (M' = Zn(II), 6; Fe(II) low-spin, 7) complexes were fit to a Curie-Weiss law (theta = -2.43 cm(-1) for 6 and theta = -0.51 cm(-1) for 7). No intramolecular radical-radical interaction is apparent in any of these complexes.

  DOI：

  10.1021/ic9803412
• 作为产物：
  描述：

  2,2'-联吡啶-6,6'-二甲醛 在 sodium periodate 作用下， 以 甲醇 为溶剂， 生成 6,6'-bis(4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl 2-yl)-2,2'-bipyridine
  参考文献：
  名称：

  Synthesis, coordination and magnetic properties of a novel family of stable chelate based biradicals: molecular structure of a 2,2′-bipyridine N-oxide N-oxyl biradical and its copper(II) complex

  摘要：

  多元（醛+羟胺）缩合后轻度氧化，生成螯合N-氧化物N-氧自由基3和6；两种配体均生成单核铜（II）和镍（II）配合物，与两个自由基配位，在低温下表现出强烈的反铁磁耦合。

  DOI：

  10.1039/c39940000741

文献信息

• Synthesis of stable free radicals: A novel family of oligopyridine based nitronyl-nitroxide biradicals
  作者：Gilles Ulrich、Raymond Ziessel、Dominique Luneau、Paul Rey

  DOI：10.1016/0040-4039(94)88026-3

  日期：1994.2

  9-dicarboxyaldehyde-1,10-phenanthroline react with N,N′-dihydroxy-2,3-diamino-2,3-dimethylbutane to yield the bis-N,N′-dihydroxyimidazolidine. Mild oxidation afforded the corresponding nitronyl-nitroxide biradicals 1 to 7. These ligands are highly colored and form very stable transition metal complexes.

  二甲酰基取代的吡啶（在2,5和2,6位），2,2'-联吡啶（在4,4'，5,5'和6,6'位），3,6-di-（ 6-羧基醛-2-吡啶基）-哒嗪和2,9-二羧基醛-1,10-菲咯啉与N，N'-二羟基-2,3-二氨基-2,3-二甲基丁烷反应生成双-N，N ′-二羟基咪唑烷。轻度氧化得到相应的亚硝酰基-硝基氧双自由基1至7。这些配体是高度着色的，并形成非常稳定的过渡金属络合物。
• Oligopyridine bis(nitronyl nitroxides): synthesis, structures, electrochemical, magnetic and electronic properties
  作者：Raymond Ziessel、Gilles Ulrich、Raphael C. Lawson、Luis Echegoyen

  DOI：10.1039/a810044f

  日期：——

  A family of pyridine, 2,2′-bipyridine, 1,10-phenanthroline, 3,6-bis(2-pyridyl)pyridazine ligands bearing two nitronyl nitroxide radicals was synthesized and characterized. The pincer ligands having two radicals in ortho positions relative to the nitrogen atoms form stable nickel(II) and copper(II) complexes. The pyridine based 2,6- and 2,5-biradicals crystallized in the monoclinic space group P2 1 /c while the bipyridine 5,5′-biradical crystallized in the monoclinic space group P2 1 /n (radical is 4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl). The highest dihedral angle between the radicals and the pyridine ring is found in the pyridine 2,6-biradical (ca. 47°), followed by the 2,5-biradical (ca. 38°) and then by the bipyridine 6,6′- (ca. 27°) and 5,5′-biradicals (ca. 24°). All the biradicals exhibit similar EPR spectra, in solution and at room temperature, with nine lines due to coupling of the unpaired electrons with four equivalent nitrogen nuclei (hyperfine coupling constant A N 3.3-3.8 G). In some cases these nine lines are reduced to five lines (A N 7.5-7.6 G) at low temperature due to a weakening of the spin-spin exchange interaction J which becomes smaller than the isotropic coupling constant. The χT  product for all radicals measured at 300 K lies in the range of 0.70-0.77 emu K mol –1 . For the pyridine 2,6- and 2,5-biradicals, magneto-structural correlation reveals through bond ferro- and antiferro-magnetic interaction (J/k B =+9.4 and –39 K, respectively) due to a favorable spin polarization effect. These intramolecular interactions persist when the radicals are dispersed in a polystyrene matrix. For the bipyridine 6,6′- and 5,5′-biradicals, the experimental data were fitted using a Bleaney-Bowers expression for two interacting spins and the values of J/k B =–24 to –1.9 K, respectively, are representative of an antiferromagnetic through-space interaction between two neighboring radicals. No intramolecular magnetic interactions were found in the oligopyridine based compounds. In all of these biradicals, both nitroxides are oxidized at the same potential (ca. +0.45 V vs. Ag/Ag + ) by a two-electron quasi-reversible process to the nitrosonium dication and irreversibly reduced to the dianions between –1.80 and –1.40 V. In the Cu(II) and Ni(II) complexes of the bipyridine-6,6′- and phenanthroline-2,9-biradical reduction of the nitroxides to the hydroxylamine anions is quasi-reversible and is facilitated by ca. 1.20 V versus the

  我们合成了一系列吡啶、2,2′-联吡啶、1,10-菲罗啉、3,6-双（2-吡啶基）哒嗪配体，并对其进行了表征。钳状配体的两个基相对于氮原子处于正交位置，形成稳定的镍（II）和铜（II）配合物。基于吡啶的 2,6- 和 2,5- 双自由基在单斜空间群 P2 1 /c 中结晶，而双吡啶的 5,5′- 双自由基在单斜空间群 P2 1 /n 中结晶（自由基为 4,4,5,5- 四甲基咪唑啉 3- 氧 1-氧）。吡啶 2,6-双烷基与吡啶环之间的二面角最大（约 47°），其次是 2,5-双烷基（约 38°），然后是双吡啶 6,6′-（约 27°）和 5,5′-双烷基（约 24°）。在溶液中和室温下，所有双缩醛都显示出类似的 EPR 光谱，其中有九条线是由于未配对电子与四个等效氮核的耦合（超频耦合常数 A N 3.3-3.8 G）造成的。在某些情况下，由于自旋-自旋交换相互作用 J 变弱（小于各向同性耦合常数），这九条线在低温下减弱为五条线（A N 7.5-7.6 G）。在 300 K 温度下测量的所有自由基的 χT 乘积范围为 0.70-0.77 emu K mol -1 。对于吡啶 2,6-和 2,5-双自由基，由于有利的自旋极化效应，磁结构相关性显示了通过键的铁磁性和反铁磁性相互作用（J/k B =+9.4 和 -39 K）。当自由基分散在聚苯乙烯基体中时，这些分子内相互作用仍然存在。对于联吡啶 6,6′- 和 5,5′- 双自由基，实验数据使用两个相互作用自旋的 Bleaney-Bowers 表达式进行拟合，J/k B =-24 至 -1.9 K 的值分别代表两个相邻自由基之间的反铁磁性通空间相互作用。在低聚吡啶化合物中没有发现分子内磁性相互作用。在所有这些双烷基化合物中，两种硝基氧化物在相同的电位（对 Ag/Ag + 的电位约为 +0.45 V）下通过双电子准可逆过程氧化成硝基锍二阳离子，并在 -1.80 和 -1.40 V 之间不可逆地还原成二阳离子。在联吡啶-6,6′- 和菲罗啉-2,9-双酰胺的 Cu(II) 和 Ni(II) 复合物中，亚硝基还原成羟胺阴离子的过程是准可逆的，与 Ag/Ag + 相比，约为 1.20 V。
• Structural control of ferromagnetic interactions in nickel(II) complexes based on a tetradentate biradical
  作者：Francisco M. Romero、Raymond Ziessel、Dominique Luneau

  DOI：10.1039/a707350j

  日期：——

  Complexation of a bipyridine-based nitronyl nitroxide biradical with nickel(II) affords two complexes that differ by the nature of one axial ligand and by their magnetic behaviour: in both cases ferromagnetic interactions between high-spin nickel(II) and the radicals are observed.

  双吡啶基硝基亚硝基自由基与镍（II）的络合生成两种络合物，它们之间的区别在于一种轴向配体的性质及其磁行为：在这两种情况下，高自旋镍（II）与自由基之间都存在铁磁相互作用。