bis<2,2'-(1-oxyl-3-oxido-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl)> | 25105-77-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: bis<2,2'-(1-oxyl-3-oxido-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl)>
• 英文别名: bis(2,2'-(1-oxyl-3-oxido-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl))；2,2'-bis(4,4,5,5-tetramethylimidazolin-1-oxyl-3-oxide)；bis[2,2'-(1-oxyl-3-oxido-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl)]
• CAS: 25105-77-5
• 化学式: C₁₄H₂₄N₄O₄
• 分子量: 312.369
• InChiKey: VUVOJVOYFVYQMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.24
• 重原子数：
  22.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  98.42
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  bis(hexafluoroacetylacetonazo)nickel(II) 、 bis<2,2'-(1-oxyl-3-oxido-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl)> 以 乙醚 、 二氯甲烷 为溶剂， 以15.9%的产率得到bis(2,2'-(1-oxyl-3-azido-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl))
  参考文献：
  名称：

  Experimental Evidence for the Triplet-Like Spin State Appearing in Ground-State Singlet Biradicals as a Key Feature for Generalized Ferrimagnetic Spin Alignment

  摘要：

  The authors have previously proposed a theoretical model for exotic spin alignment in organic molecular assemblages: The alternating chain of organic biradicals in a singlet (S-b = 0) ground state and monoradicals with S = 1/2 has a ferrimagnetic ground state for the whole chain, which has been termed generalized ferrimagnetism. An important feature of the generalized ferTimagnetic spin alignment has been found in the deviation of the expectation value < Sb-2 > of the biradical spin from zero. Even a triplet-like spin state (Sb 2) = 2 (Sb = 1) has been predicted in the theoretical calculations. In this study, we have found experimental evidence for the pseudo-triplet state appearing in the ground-state singlet biradical of a real open-shell compound. At first, we have demonstrated from theoretical calculations that the singlet biradical has (Sb 2) = 2 (Sb = 1) in a molecular pair with an S = 1 metal ion as well as with the S = 1/2 monoradical. The pseudo-triplet state of the biradical affords a singlet state of the whole system of the biradical-metal ion pair, which is readily detectable in experiments for verifying the theoretical prediction. As a model compound for the biradical-metal ion pair, a transition metal complex, [(bnn)(Ni(hfac)(2))(1.5)(H2O)] (1), has been synthesized from a nitronyl nitroxide-based ground-state singlet biradical bnn and Ni(hfach). From X-ray crystallographic analyses, the compound contains a molecular pair of bnn and Ni(hfac)(2), which serves as a model system under the above theoretical studies. It has been found from the analysis of the temperature dependence of magnetic susceptibility that the bnn-Ni(hfac)(2) pair has the singlet (S = 0) ground state. The singlet ground state of the pair results from an antiparallel coupling of the pseudo-triplet of the biradical and the S = 1 spin on the Ni ion. The pseudo-triplet state in the ground-state singlet biradical has thus been verified experimentally, which is crucially important to realize the generalized ferrimagnetic spin alignment.

  DOI：

  10.1021/jp056052y
• 作为产物：
  描述：

  (dinitroxide carbene)OTf 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 以34%的产率得到bis<2,2'-(1-oxyl-3-oxido-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl)>
  参考文献：
  名称：

  Dinitroxide Carbenes, A New Class of Carbenes with Autoumpolung Character: Preparation in Solution and Stabilization in Transition Metal Complexes We thank Prof. P. Audebert, ENS Cachan (Paris), for undertaking the cyclic voltammetric measurements and Dr. F. Hampel, Universität Erlangen-Nürnberg, for performing the crystal-structure analysis.

  摘要：

  DOI：

  10.1002/1521-3773(20020118)41:2<311::aid-anie311>3.0.co;2-l

文献信息

• A Spin-Frustrated System Composed of Organic Radicals and Magnetic Metal Ions
  作者：Megumi Tanaka、Kenji Matsuda、Tetsuji Itoh、Hiizu Iwamura

  DOI：10.1002/(sici)1521-3773(19980403)37:6<810::aid-anie810>3.0.co;2-q

  日期：1998.4.3

  Despite antiferromagnetic coupling between any two neighboring spins, parallel alignment of the 3d spins of the MnII ions and the 2p spins of the organic ligand is observed for the (degenerate) ground state of [Mn(hfac)2 }2 (bnn)] (shown on the right). The "butterfly"-shaped arrangement of the spins contributes to this noteworthy spin configuration. hfac=hexafluoroacetylacetonate, bnn=2,2'-bis(1-oxyl-3-oxide-4,4,5,5-tetramethylimidazolinyl).