1,3,5-Trithia-2,4,6-triazapentalenyl | 121143-50-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1,3,5-Trithia-2,4,6-triazapentalenyl
• 英文别名: 1,3,5-trithia-2,4,6-triazapentalenyl radical
• CAS: 121143-50-8
• 化学式: C₂N₃S₃
• 分子量: 162.24
• InChiKey: VNODSPFVIAZZGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  106
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  六氟乙酰丙酮化铜的水合物 、 1,3,5-Trithia-2,4,6-triazapentalenyl 以 正庚烷 为溶剂， 生成 (1,3,5-trithia-2,4,6-triazapentalenyl)(bis(hexafluoroacetylacetonato)copper(II))
  参考文献：
  名称：

  铁磁配位聚合物由杂环噻唑基，1,3,5-三硫杂-2,4,6-三氮杂戊烯基（TTTA）和双（六氟乙酰丙酮基）铜（II）（Cu（hfac）（2））组成。

  摘要：

  DOI：

  10.1021/ja002873z
• 作为产物：
  描述：

  2-Chloro-2lambda4,4,7-trithia-3,6,8-triazabicyclo[3.3.0]octa-1(8),2,5-triene 生成 1,3,5-Trithia-2,4,6-triazapentalenyl
  参考文献：
  名称：

  WOLMERSHAUSER, GOTTHELF;JOHANN, RUDOLF, ANGEW. CHEM., 101,(1989) N, C. 952-953

  摘要：

  DOI：

文献信息

• Synthesis, crystal structures, electronic structure and magnetic behaviour of the trithiatriazapentalenyl radical, C2S3N3
  作者：Gordon D. McManus、Jeremy M. Rawson、Neil Feeder、Joost van Duijn、Eric J. L. McInnes、Juan J. Novoa、Ramon Burriel、Fernando Palacio、Patricia Oliete

  DOI：10.1039/b103303b

  日期：——

  A novel synthesis of the title compound, C2S3N3 (1) is reported. X- and K-band EPR spectra on dilute solutions of 1 indicate delocalisation of the unpaired spin density over both heterocyclic rings in agreement with DFT calculations. An XRPD study indicates that it crystallises in two morphologies with both phases formed during vacuum sublimation. The XRPD studies indicate that on cooling below 230 K, only the triclinic phase (P) becomes detectable, whereas on warming above 320 K, just the monoclinic phase (P21/c) becomes observed. The crystal structure of the monoclinic phase has been examined by variable temperature single crystal X-ray diffraction in the region 300–225 K and reveals a regular π-stacked structure. A crystal structure of the triclinic phase is reported at 150 K and exhibits a dimeric π-stacked motif. Susceptibility measurements show that the monoclinic phase is paramagnetic whereas the triclinic phase is diamagnetic. This radical exhibits thermal hysteresis with a wide range of bistability; EPR and magnetic susceptibility measurements indicate Tc↓ = 234 K, and Tc↑ = 317 K. The magnetic behaviour of the monoclinic phase is consistent with strong antiferromagnetic exchange interactions between open shell doublet states (J = −320 K) along the π-stacking direction, although significant inter-stack interactions are required to model the data adequately. In contrast the dimeric phase is essentially diamagnetic, with the residual paramagnetism indicating a very large singlet–triplet separation (|2J| > 2000 K). The magnetic exchange interactions in both phases are probed through a series of DFT calculations using the broken-symmetry approach. These confirm the presence of strong magnetic exchange interactions along the π-stacking direction in the high temperature phase (2J = −182 K), but with additional interstack interactions which are an order of magnitude smaller. Calculations on the triclinic phase indicate that it is best considered as a dimer with an open-shell singlet state with a very large singlet–triplet separation (2J = −2657 K). The magnitude of J for both phases from theory and experiment are in good agreement. The origin of the thermal hysteresis is attributed to the presence of two energetically similar structures which have a low energy barrier to interconversion. The thermodynamic parameters associated with the interconversion process have been probed by DSC studies. It confirms the first order nature of the transition with Tc↓ = 232.3 K (ΔH↓ = 1.41 kJ mol−1, ΔS↓ = 6.0 J mol−1 K−1) and Tc↑ = 320.5 K (ΔH↑ = 1.86 kJ mol−1, ΔS↑ = 5.8 J mol−1 K−1).

  晶体结构的研究表明，在230 K以下冷却时，只有三斜相（P）可被检测到，而在320 K以上加热时，只有单斜相（P21/c）可被观察到。通过在300-225 K范围内进行可变温度单晶X射线衍射，对单斜相的晶体结构进行了研究，并揭示了一种规则的π堆积结构。在150 K时，三斜相的晶体结构被报道，并呈现出二聚体π堆积图案。磁化率测量表明，单斜相为顺磁性，而三斜相为反磁性。该自由基表现出具有宽双稳态的热滞后；EPR和磁化率测量表明Tc↓ = 234 K，Tc↑ = 317 K。单斜相的磁性行为与沿π堆积方向上的开壳双态（J = -320 K）之间的强反铁磁交换相互作用一致，尽管需要显著的堆栈间相互作用来充分模拟数据。相比之下，二聚体相基本上是反磁性的，残留的顺磁性表明单线态和三线态的分离非常大（|2J|> 2000 K）。通过一系列使用破对称方法的DFT计算，研究了两个相中的磁交换相互作用。这些证实了高温相（2J = -182 K）中沿π堆积
• Wolmershaeuser, Gotthelf; Johann, Rudolf, Angewandte Chemie, 1989, vol. 101, # 7, p. 952 - 953
  作者：Wolmershaeuser, Gotthelf、Johann, Rudolf

  DOI：——

  日期：——
• WOLMERSHAUSER, GOTTHELF;JOHANN, RUDOLF, ANGEW. CHEM., 101,(1989) N, C. 952-953
  作者：WOLMERSHAUSER, GOTTHELF、JOHANN, RUDOLF

  DOI：——

  日期：——
• Ferromagnetic Coordination Polymer Composed of Heterocyclic Thiazyl Radical, 1,3,5-Trithia-2,4,6-triazapentalenyl (TTTA), and Bis(hexafluoroacetylacetonato)copper(II) (Cu(hfac)₂)
  作者：Wataru Fujita、Kunio Awaga

  DOI：10.1021/ja002873z

  日期：2001.4.1