1,3,5-tris(p-(N-oxy-N-tert-butylamino)phenyl)benzene | 151799-76-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,3,5-tris(p-(N-oxy-N-tert-butylamino)phenyl)benzene
• 英文别名: 1,3,5-tris-(p-(N-t-butyl-N-oxyamino)phenyl)benzene
• CAS: 151799-76-7
• 化学式: C₃₆H₄₂N₃O₃
• 分子量: 564.748
• InChiKey: CZWSRHOLQNSWBS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  42
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  manganese bis(1,1,1,5,5,5-hexafluoroacetylacetonato) dihydrate 、 1,3,5-tris(p-(N-oxy-N-tert-butylamino)phenyl)benzene 以 乙醚 、 正庚烷 、 苯 为溶剂， 生成
  参考文献：
  名称：

  Tacticity versus dimension of the extended structures in the crystals of heterospin magnets made of transition-metal complexes with the poly(aminoxyl) radical

  摘要：

  双（氨基氧）和三（氨基氧）自由基以及二（4-吡啶基）重氮甲烷与 [M(hfac)2]（M=锰Ⅱ或铜Ⅱ，hfac=六氟乙酰丙酮）反应后形成具有扩展结构的结晶络合物。这些复合物中的有机 2p 和金属 3d 自旋在 3.4-46 K 下有序，这取决于扩展结构的尺寸和相邻自旋之间交换耦合的大小。在一维系统的晶体中，聚合物链是同向的，即自由基或前体配体和/或金属中心在任何给定的链上都具有相同的手性。聚合链是双向的，交叉连接形成二维蜂巢或三维交叉平行网络。

  DOI：

  10.1039/a707641j
• 作为产物：
  描述：

  1,3,5-三(4-溴苯基)苯 在 亚硝基叔丁烷 、 silver(l) oxide 作用下， 以 四氢呋喃 、 正己烷 、 氯仿 为溶剂， 反应 6.0h， 生成 1,3,5-tris(p-(N-oxy-N-tert-butylamino)phenyl)benzene
  参考文献：
  名称：

  Persistent 1,3,5-benzenetriyltris(N-tert-butyl nitroxide) and its analogs with quartet ground states. Intramolecular triangular exchange coupling among three nitroxide radical centers

  摘要：

  1,3,5-Benzenetriyltris(N-tert-butyl nitroxide (3), its 2-methoxy derivative (4), and 1,3,5-tris{ip-(N-oxy-N-tert-butylamino)phenyl}benzene (5) were prepared and studied by EPR and magnetic susceptibility/magnetization measurements. Trinitroxides 3 and 4 showed EPR fine structures characteristic of quartet states: 3: g = 2.0062, \D/hc\ = 0.009 32 cm-1 and \E/hc\ = 0.000 15 cm-1; 4: g = 2.0063, \D/hc\ = 0.009 66 cm-1 and \E/hc\ = 0.000 32 cm-1. The changes in the signal intensity vs reciprocal temperature obeyed Curie's law in the range 10-100 K, suggesting that the quartets are their ground states. Magnetization data for 3 and 4 at 1.8, 3.0, and 4.0 K in the field range 0-7 T obeyed the Brillouin function in which S = 3/2. The effective magnetic moment of a crystalline sample of 4 obtained on a SQUID susceptometer was 3.21 mu(B) at 240 K, increased gradually, reached a maximum (mu(eff)/mu(B) = 3.73) at 32 K, and decreased steeply as the temperature was decreased. The results were interpreted in terms of an isosceles-triangular exchange interaction among the three nitroxide radicals within a molecule (J1/k(B) = 68.4 and J2/k(B) = 5.0 K) and antiferromagnetic intermolecular interaction (theta = -1.7 K). A methoxy group on the m-phenylene ring was found to weaken the through-ring exchange coupling among the attached nitroxide radicals by an order of magnitude. An X-ray structure analysis of a clear red block cubic single crystal of 5, Pa3BAR (No. 205), a = 18.786(2) angstrom, V = 6631(2) angstrom3, Z = 8, D(calc) = 1.301 g cm-3, revealed the molecular structure with three nitroxide groups 37.5-degrees out of the peripheral p-phenylene rings which am tilted out of the central benzenetriyl unit by 19.5-degrees in a propeller conformation. Temperature dependences of the mu(eff) values observed for crystalline and matrix-isolated 5 in the range 5-300 K gave J/k(B) values of +6.8 K (theta = -2.1 K) and +5.3 K, respectively, when analyzed in terms of a regular-triangular exchange coupling model. Lower spin polarization on the 1,3,5-triphenylbenzene chromophore is concluded to be responsible for the reduced J value in 5.

  DOI：

  10.1021/j100152a034

文献信息

• Inoue, Katsuya; Iwamura, Hiizu, Journal of the American Chemical Society, 1994, vol. 116, # 7, p. 3173 - 3174
  作者：Inoue, Katsuya、Iwamura, Hiizu

  DOI：——

  日期：——
• Persistent 1,3,5-benzenetriyltris(N-tert-butyl nitroxide) and its analogs with quartet ground states. Intramolecular triangular exchange coupling among three nitroxide radical centers
  作者：Fumio Kanno、Katsuya Inoue、Noboru Koga、Hiizu Iwamura

  DOI：10.1021/j100152a034

  日期：1993.12

  1,3,5-Benzenetriyltris(N-tert-butyl nitroxide (3), its 2-methoxy derivative (4), and 1,3,5-trisip-(N-oxy-N-tert-butylamino)phenyl}benzene (5) were prepared and studied by EPR and magnetic susceptibility/magnetization measurements. Trinitroxides 3 and 4 showed EPR fine structures characteristic of quartet states: 3: g = 2.0062, \D/hc\ = 0.009 32 cm-1 and \E/hc\ = 0.000 15 cm-1; 4: g = 2.0063, \D/hc\ = 0.009 66 cm-1 and \E/hc\ = 0.000 32 cm-1. The changes in the signal intensity vs reciprocal temperature obeyed Curie's law in the range 10-100 K, suggesting that the quartets are their ground states. Magnetization data for 3 and 4 at 1.8, 3.0, and 4.0 K in the field range 0-7 T obeyed the Brillouin function in which S = 3/2. The effective magnetic moment of a crystalline sample of 4 obtained on a SQUID susceptometer was 3.21 mu(B) at 240 K, increased gradually, reached a maximum (mu(eff)/mu(B) = 3.73) at 32 K, and decreased steeply as the temperature was decreased. The results were interpreted in terms of an isosceles-triangular exchange interaction among the three nitroxide radicals within a molecule (J1/k(B) = 68.4 and J2/k(B) = 5.0 K) and antiferromagnetic intermolecular interaction (theta = -1.7 K). A methoxy group on the m-phenylene ring was found to weaken the through-ring exchange coupling among the attached nitroxide radicals by an order of magnitude. An X-ray structure analysis of a clear red block cubic single crystal of 5, Pa3BAR (No. 205), a = 18.786(2) angstrom, V = 6631(2) angstrom3, Z = 8, D(calc) = 1.301 g cm-3, revealed the molecular structure with three nitroxide groups 37.5-degrees out of the peripheral p-phenylene rings which am tilted out of the central benzenetriyl unit by 19.5-degrees in a propeller conformation. Temperature dependences of the mu(eff) values observed for crystalline and matrix-isolated 5 in the range 5-300 K gave J/k(B) values of +6.8 K (theta = -2.1 K) and +5.3 K, respectively, when analyzed in terms of a regular-triangular exchange coupling model. Lower spin polarization on the 1,3,5-triphenylbenzene chromophore is concluded to be responsible for the reduced J value in 5.
• Tacticity versus dimension of the extended structures in the crystals of heterospin magnets made of transition-metal complexes with the poly(aminoxyl) radical
  作者：Hiizu Iwamura、Katsuya Inoue、Noboru Koga

  DOI：10.1039/a707641j

  日期：——

  Bis- and tris(aminoxyl) radicals and di(4-pyridyl)diazomethane form crystalline complexes with extended structures upon reaction with [M(hfac)2] (M=MnII or CuII, and hfac=hexafluoroacetylacetonate). Organic 2p and metal 3d spins in these complexes order at 3.4–46 K depending on the dimensions of the extended structures and the magnitude of exchange coupling between the adjacent spins. In the crystals of one-dimensional systems, the polymeric chains are isotactic in that free radical or precursor ligands and/or metal centres have the same chirality along any given chain. The polymeric chains are syndiotactic and cross link to form two-dimensional honeycomb or three-dimensional crossed parallel networks.

  双（氨基氧）和三（氨基氧）自由基以及二（4-吡啶基）重氮甲烷与 [M(hfac)2]（M=锰Ⅱ或铜Ⅱ，hfac=六氟乙酰丙酮）反应后形成具有扩展结构的结晶络合物。这些复合物中的有机 2p 和金属 3d 自旋在 3.4-46 K 下有序，这取决于扩展结构的尺寸和相邻自旋之间交换耦合的大小。在一维系统的晶体中，聚合物链是同向的，即自由基或前体配体和/或金属中心在任何给定的链上都具有相同的手性。聚合链是双向的，交叉连接形成二维蜂巢或三维交叉平行网络。