tetrakis(2-pyridyl-N-oxidemethylthio)tetrathiafulvalene | 1418219-70-1

• 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: tetrakis(2-pyridyl-N-oxidemethylthio)tetrathiafulvalene
• 英文别名: 2-[[2-[4,5-Bis[(1-oxidopyridin-1-ium-2-yl)methylsulfanyl]-1,3-dithiol-2-ylidene]-5-[(1-oxidopyridin-1-ium-2-yl)methylsulfanyl]-1,3-dithiol-4-yl]sulfanylmethyl]-1-oxidopyridin-1-ium
• CAS: 1418219-70-1
• 化学式: C₃₀H₂₄N₄O₄S₈
• 分子量: 761.073
• InChiKey: BKVDXACJASGZPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  46
• 可旋转键数：
  12
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  304
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  氯仿 、 dysprosium(III) 1,1,1,5,5,5-hexafluoroacetylacetonate dihydrate 、 tetrakis(2-pyridyl-N-oxidemethylthio)tetrathiafulvalene 反应 0.25h， 以73%的产率得到[Dy₄(1,1,1,5,5,5-hexafluoroacetylacetonate)₁₂(tetrakis(2-pyridyl-N-oxidemethylthio)tetrathiafulvalene)₂]*2chloroform
  参考文献：
  名称：

  High Nuclearity Complexes of Lanthanide Involving Tetrathiafulvalene Ligands: Structural, Magnetic, and PhotoPhysical Properties

  摘要：

  The reaction between the tetrakis(2-pyridyl-N-oxidemethylthio)-tetrathiafulvalene ligand (L) and Ln(hfac)(3)center dot 2H(2)O precursors (where hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate anion and Ln = Tb-III (1), Dy-III (2), Er-III (3), and Yb-III (4) and (4b)) leads to the formation of five tetranuclear complexes of formula [Ln(4)(hfac)(12)(L)(2)]center dot xCHCl(3).yC(6)H(14) (n = 1, x = 2, y = 0 for (1), (2), and (4), n = 1, x = 4 for (3), and n = 2, x = 2.5, y = 1 for (4b)). Their X-ray structures reveal that the surrounding of each Ln(III) center is filled by two N-oxide groups coming from two different ligands L. These tetranuclear complexes have the highest nuclearity which is reported until now for coordination compounds of lanthanide involving TTF-based ligands. Direct current (dc) measurements highlight the paramagnetic behavior of the compounds with a significant crystal field effect. The temperature dependences of static magnetic measurements for 4 have been fitted. The ground state corresponds to M-J = +/- 5/2 while the first excited state (M-J = +/- 3/2) was localized at +214 cm(-1) which was well correlated with the luminescence transition. UV-visible absorption properties have been experimentally measured and rationalized by time-dependent density functional theory (TD-DFT) calculations. Upon irradiation at 77 K and room temperature, in the range 24390-20835 cm(-1), both compounds 3 and 4 display a metal-centered luminescence attributed to I-4(13/2) -> I-4(15/2) (6660 cm(-1)) and F-2(5/2) -> F-2(7/2) (signal centered around the value of 9966 cm(-1)) transitions, respectively. The observed six transitions could be attributed to the M-J state splitting due to the existence of two Yb1 and Yb2 ions with slightly different polyhedra in 4.

  DOI：

  10.1021/ic302532f
• 作为产物：
  描述：

  2,3,6,7-四(2-氰乙基硫代)四硫富瓦烯 、 2-(氯甲基)-1-氧代吡啶-1-鎓 在 sodium ethanolate 作用下， 以 乙醇 为溶剂， 反应 22.0h， 以62%的产率得到tetrakis(2-pyridyl-N-oxidemethylthio)tetrathiafulvalene
  参考文献：
  名称：

  High Nuclearity Complexes of Lanthanide Involving Tetrathiafulvalene Ligands: Structural, Magnetic, and PhotoPhysical Properties

  摘要：

  The reaction between the tetrakis(2-pyridyl-N-oxidemethylthio)-tetrathiafulvalene ligand (L) and Ln(hfac)(3)center dot 2H(2)O precursors (where hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate anion and Ln = Tb-III (1), Dy-III (2), Er-III (3), and Yb-III (4) and (4b)) leads to the formation of five tetranuclear complexes of formula [Ln(4)(hfac)(12)(L)(2)]center dot xCHCl(3).yC(6)H(14) (n = 1, x = 2, y = 0 for (1), (2), and (4), n = 1, x = 4 for (3), and n = 2, x = 2.5, y = 1 for (4b)). Their X-ray structures reveal that the surrounding of each Ln(III) center is filled by two N-oxide groups coming from two different ligands L. These tetranuclear complexes have the highest nuclearity which is reported until now for coordination compounds of lanthanide involving TTF-based ligands. Direct current (dc) measurements highlight the paramagnetic behavior of the compounds with a significant crystal field effect. The temperature dependences of static magnetic measurements for 4 have been fitted. The ground state corresponds to M-J = +/- 5/2 while the first excited state (M-J = +/- 3/2) was localized at +214 cm(-1) which was well correlated with the luminescence transition. UV-visible absorption properties have been experimentally measured and rationalized by time-dependent density functional theory (TD-DFT) calculations. Upon irradiation at 77 K and room temperature, in the range 24390-20835 cm(-1), both compounds 3 and 4 display a metal-centered luminescence attributed to I-4(13/2) -> I-4(15/2) (6660 cm(-1)) and F-2(5/2) -> F-2(7/2) (signal centered around the value of 9966 cm(-1)) transitions, respectively. The observed six transitions could be attributed to the M-J state splitting due to the existence of two Yb1 and Yb2 ions with slightly different polyhedra in 4.

  DOI：

  10.1021/ic302532f