tetrabutylammonium 4,8-dioxo-4H,8H-dibenzopyren-12-olate

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: tetrabutylammonium 4,8-dioxo-4H,8H-dibenzopyren-12-olate
• 英文别名: 14,22-Dioxohexacyclo[11.7.1.13,19.02,7.09,21.015,20]docosa-1(21),2(7),3,5,8,10,12,15,17,19-decaen-8-olate;tetrabutylazanium
• 化学式: C₁₆H₃₆N*C₂₂H₉O₃
• 分子量: 563.78
• InChiKey: MKYIMAILHNANKV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.52
• 重原子数：
  42
• 可旋转键数：
  12
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  57.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tetrabutylammonium 4,8-dioxo-4H,8H-dibenzopyren-12-olate 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 1.67h， 以88%的产率得到4,8-dioxo-4H,8H-dibenzo[cd,mn]pyren-12-oxyl
  参考文献：
  名称：

  Trioxotriangulene: Air- and Thermally Stable Organic Carbon-Centered Neutral π-Radical without Steric Protection

  摘要：

  有机中性自由基在空气中通常是非常不稳定的化学物种，要使其稳定，"立体保护 "是最普遍也是最不可或缺的方法。在设计多环碳心π自由基电子自旋结构的基础上，我们首次实现了一种特殊稳定的无笨重取代基的中性π自由基--4,8,12-三氧杂三羰基（TOT），它在空气中的固态分解点高于 240 ℃。作为一种中性自由基，TOT 在空气中具有极高的稳定性，这得益于其对称和扩展的 π 电子结构所产生的自旋定位。位于中心碳原子上的最大电子自旋密度会进一步降低外围碳原子的自旋密度。在溶液状态下，TOT 处于单体和高度对称的 π 二聚体之间的平衡状态，并通过形成强双电子多中心键而得到稳定。晶体结构分析表明，TOT 衍生物具有很强的自组装能力，可形成一维柱状，由于不含笨重的取代基团，柱间的多种非共价相互作用可进一步构建三维网络。位于 TOT 三角形碳框架顶点的取代基团可改变一维柱中的π堆叠模式，从而影响磁性和近红外区域的光吸收。取代基团的电子效应也会影响 TOT 的氧化还原电位。在我们的研究中，TOT 中性自由基具有奇特的高稳定性，其三维网络通过强有力的分子间相互作用而实现，这对新的多环空气稳定中性自由基的分子设计非常有益。此外，我们相信，中性π自由基的开壳电子结构与闭壳分子体系的开壳电子结构截然不同，这也将为探索由其非常规电子自旋性质所产生的特殊物理性质和有机转化催化活性带来里程碑式的意义。

  DOI：

  10.1246/bcsj.20180074
• 作为产物：
  描述：

  四丁基氢氧化铵 、 potassium 4,8-dioxo-4H,8H-dibenzopyren-12-olate 在 盐酸 作用下， 生成 tetrabutylammonium 4,8-dioxo-4H,8H-dibenzopyren-12-olate
  参考文献：
  名称：

  Allinson, Graeme; Bushby, Richard J.; Paillaud, Jean-Louis, Journal of the Chemical Society. Perkin transactions I, 1995, # 4, p. 385 - 390

  摘要：

  DOI：

文献信息

• The synthesis of singlet ground state derivatives of non-Kekulé polynuclear aromatics
  作者：Graeme Allinson、Richard J. Bushby、Malini V. Jesudason、Jean-Louis Paillaud、Norman Taylor

  DOI：10.1039/a606932k

  日期：——

  It is known that a two-electron reduction of tetrabutylammonium 3,4-dioxo-4H,8H-dibenzo[cd,mn]pyren- 12-olate gives a trioxy (tri-O-) derivative of the non-Kekulé polynuclear aromatic compound dibenzo[cd,mn]pyrene (triangulene). This derivative is stable in solution and, like triangulene itself, has a triplet ground state. In exploring the generality of this strategy for the synthesis of high-spin derivatives of non-Kekulé polynuclear aromatic compounds we have investigated two electron reductions of 4,8-dioxo-4H,8H-dibenzo[cd,mn]pyrene (to give a dioxy derivative of triangulene), 7,8-dioxo-7H,8H-dibenzo[de,hi ]naphthacene (to give a dioxy derivative of dibenzo[de,hi]naphthacene) and 7,9-dioxo-7H,9H-dibenzo[de,jk ]pentacene (to give a dioxy derivative of dibenzo[de,jk]pentacene). Dibenzo[cd,mn]pyrene (triangulene), dibenzo[de,hi]naphthacene and dibenzo[de,jk]pentacene should all have triplet ground states, but the presence of two O- substituents on these aromatic nuclei will (just) lift the degeneracy of the putative singly occupied molecular orbitals. We have shown that the splitting this produces is sufficient to ensure that all of these dioxy derivatives have singlet ground states. Hence the strategy employed for making and stabilising triplet triangulene as its trioxy derivative does not provide a paradigm for other high-spin non-Kekulé polynuclear aromatics. The reduction reactions were studied by cyclic voltammetry, by UV–VIS spectroscopy, and by EPR spectroscopy. Improved synthetic routes are described for 7,8-dioxo-7H,8H-dibenzo[de,hi ]naphthacene and for 7,9-dioxo-7H,9H-dibenzo[de,jk ]pentacene. Violent explosions were encountered in attempts to repeat the literature procedure for the synthesis of 4,6-dichlorobenzene-1,3-dicarboxylic acid.

  已知，四丁基铵3,4-二氧-4H,8H-二苯并[cd,mn]芘-12-olate的二电子还原反应产生非Kekulé多核芳香化合物二苯并[cd,mn]芘（三角烯）的三氧（tri-O-）衍生物。这种衍生物在溶液中稳定，并且像三角烯本身一样，具有三重态基态。在探索这种策略合成非Kekulé多核芳香化合物的高自旋衍生物的普遍性时，我们研究了4,8-二氧-4H,8H-二苯并[cd,mn]芘（产生三角烯的二氧衍生物）、7,8-二氧-7H,8H-二苯并[de,hi]萘并萘（产生二苯并[de,hi]萘并萘的二氧衍生物）和7,9-二氧-7H,9H-二苯并[de,jk]戊搭烯（产生二苯并[de,jk]戊搭烯的二氧衍生物）的二电子还原反应。二苯并[cd,mn]芘（三角烯）、二苯并[de,hi]萘并萘和二苯并[de,jk]戊搭烯都应该具有三重态基态，但这些芳香核上有两个O取代基的存在（恰好）会解除假定的单占据分子轨道的简并性。我们已经证明，这种分裂产生的分裂足以确保所有这些二氧衍生物具有单重态基态。因此，用于制造和稳定三重态三角烯作为其三氧衍生物的策略并不为其他高自旋的非Kekulé多核芳香化合物提供范例。还原反应通过循环伏安法、紫外-可见光谱和电子顺磁共振光谱进行了研究。还描述了7,8-二氧-7H,8H-二苯并[de,hi]萘并萘和7,9-二氧-7H,9H-二苯并[de,jk]戊搭烯的改进合成路线。在尝试重复文献中4,6-二氯苯-1,3-二羧酸的合成步骤时，遭遇了剧烈的爆炸。
• Allinson, Graeme; Bushby, Richard J.; Paillaud, Jean-Louis, Journal of the Chemical Society. Perkin transactions I, 1995, # 4, p. 385 - 390
  作者：Allinson, Graeme、Bushby, Richard J.、Paillaud, Jean-Louis、Thornton-Pett, Mark

  DOI：——

  日期：——
• Trioxotriangulene: Air- and Thermally Stable Organic Carbon-Centered Neutral π-Radical without Steric Protection
  作者：Yasushi Morita、Tsuyoshi Murata、Akira Ueda、Chiaki Yamada、Yuki Kanzaki、Daisuke Shiomi、Kazunobu Sato、Takeji Takui

  DOI：10.1246/bcsj.20180074

  日期：2018.6.15

  To stabilize organic neutral radicals, which are usually very unstable chemical species in air atmosphere, “steric protection” is the most general and indispensable method. Based on the design of electronic-spin structure of polycyclic carbon-centered π-radicals, we have for the first time realized a peculiarly stable neutral π-radical without bulky substituent groups, 4,8,12-trioxotriangulene (TOT), whose decomposition point is higher than 240 °C in the solid state under air. This remarkably high air-stability as a neutral radical is achieved by spin-delocalization originating from the symmetric and expanded π-electronic structure of TOT. The oxo-functionalities also highly contribute to the high stability through electronic-spin modulation, where the largest electronic spin density located at the central carbon atom further decreases the spin densities of the peripheral carbon atoms. In the solution state, TOT is in the equilibrium between the monomer and highly symmetric π-dimer, as stabilized by the formation of the strong two-electron-multicenter bonding. Crystal structure analysis revealed that TOT derivatives show strong self-assembling ability forming one-dimensional columns, which further construct three-dimensional networks by multiple intercolumnar non-covalent interactions due to the absence of bulky substituent groups. Substituent groups at the apexes of the triangular carbon-framework of TOT afford variations of the π-stacking mode in the one-dimensional columns, influencing the magnetic properties and photo-absorptions around the near-infrared region. The electronic effect of the substituent groups also affects the redox potentials of TOT. The peculiarly high stability of TOT neutral radicals and their three-dimensional networks by robust intermolecular interactions achieved in our study are very beneficial for the molecular design of new polycyclic air-stable neutral radicals. Furthermore, we believe that the open-shell electronic structures of neutral π-radicals, which are quite different from those of close-shell molecular systems, will also produce milestones for the exploration of peculiar physical properties and catalytic activity for organic transformation originating from their unconventional electronic-spin nature.

  有机中性自由基在空气中通常是非常不稳定的化学物种，要使其稳定，"立体保护 "是最普遍也是最不可或缺的方法。在设计多环碳心π自由基电子自旋结构的基础上，我们首次实现了一种特殊稳定的无笨重取代基的中性π自由基--4,8,12-三氧杂三羰基（TOT），它在空气中的固态分解点高于 240 ℃。作为一种中性自由基，TOT 在空气中具有极高的稳定性，这得益于其对称和扩展的 π 电子结构所产生的自旋定位。位于中心碳原子上的最大电子自旋密度会进一步降低外围碳原子的自旋密度。在溶液状态下，TOT 处于单体和高度对称的 π 二聚体之间的平衡状态，并通过形成强双电子多中心键而得到稳定。晶体结构分析表明，TOT 衍生物具有很强的自组装能力，可形成一维柱状，由于不含笨重的取代基团，柱间的多种非共价相互作用可进一步构建三维网络。位于 TOT 三角形碳框架顶点的取代基团可改变一维柱中的π堆叠模式，从而影响磁性和近红外区域的光吸收。取代基团的电子效应也会影响 TOT 的氧化还原电位。在我们的研究中，TOT 中性自由基具有奇特的高稳定性，其三维网络通过强有力的分子间相互作用而实现，这对新的多环空气稳定中性自由基的分子设计非常有益。此外，我们相信，中性π自由基的开壳电子结构与闭壳分子体系的开壳电子结构截然不同，这也将为探索由其非常规电子自旋性质所产生的特殊物理性质和有机转化催化活性带来里程碑式的意义。