[4,5-bis(2-pyridyl-N-oxidemethylthio)]-4′,5′-methyldithiotetrathiafulvalene | 1433805-66-3

• 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: [4,5-bis(2-pyridyl-N-oxidemethylthio)]-4′,5′-methyldithiotetrathiafulvalene
• 英文别名: 4,5-bis(2-pyridyl-N-oxidemethylthio)-4′,5′-methyldithiotetrathiafulvalene；2-[[2-[4,5-Bis(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: 1433805-66-3
• 化学式: C₂₀H₁₈N₂O₂S₈
• 分子量: 574.903
• InChiKey: XBOLPDXGVKVQEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  253
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  terbium(III) 1,1,1,5,5,5-hexafluoroacetylacetonate dihydrate 、 [4,5-bis(2-pyridyl-N-oxidemethylthio)]-4′,5′-methyldithiotetrathiafulvalene 以 正庚烷 、 氯仿 为溶剂， 反应 0.25h， 以74%的产率得到[Tb₂(hfac)₆((4,5-bis(2-pyridyl-N-oxidemethylthio)-4′,5′)-methyldithiotetrathiafulvalene)₂]
  参考文献：
  名称：

  A Series of Tetrathiafulvalene-Based Lanthanide Complexes Displaying Either Single Molecule Magnet or Luminescence—Direct Magnetic and Photo-Physical Correlations in the Ytterbium Analogue

  摘要：

  The reaction between (4,5-bis(2-pyridyl-N-oxidemethylthio)-4',5')-ethylenedithiotetrathiafulvene (L-1) or -methyldithiotetrathiafulvene (L-2) ligands and Ln(hfac)(3)center dot nH(2)O precursors (Ln(III) = Pr, Tb, Dy, Er, and Yb) leads to the formation of seven dinudear complexes of formula [Ln(2)(hfac)(6)(H2O)(x)(L-y)(2)] (x = 2 and y = 1 for L-III = Pr (1); x = 0 and y = 1 for Ln(III) = Tb (2), Dy (3), Er (4) and Yb (5); x = 0 and y = 2 for Ln(III) = Tb (6) and Dy (7)). Their X-ray structures reveal that the coordination environment of each Ln(III) center is filled by two N-oxide groups coming from two different ligands L-y. UV-visible absorption properties have been experimentally measured and rationalized by TD-DFT calculations. The temperature dependences of static magnetic measurements have been fitted. The ground state corresponds to the almost pure vertical bar M-J = +/- 13/2 > while the first excited state (+/- 0.77 vertical bar +/- 11/2 > +/- 0.50 vertical bar +/- 3/2 > +/- 0.39 vertical bar +/- 5/2 >) is located at 19 cm(-1) and 26.9 cm(-1) respectively for 3 and 7. Upon irradiation at 77 K and at room temperature, in the range 25 000-20 835 cm(-1), both compounds 4 and 5 display a metal-centered luminescence attributed to I-4(13/2) -> I-4(15/2) (6660 cm(-1)) and F-2(5/2) -> E-2(7/2) (9972 cm(-1)) transitions, respectively. Emission spectroscopy provides a direct probe of the vertical bar +/- 5/2 > ground state multiplet splitting, which has been confronted to magnetic data. The energy separation of 225 cm(-1) between the ground state and the first excited level (M-J = +/- 3/2) fits exactly the second emission line (234 cm(-1)). While no out-phase-signal is detected for 3, the change of ligand L-1 -> L-2 induces a change of coordination sphere symmetry around the Dy-III increasing the energy splitting between the ground and first excited states, and 7 displays a single molecule magnet behavior.

  DOI：

  10.1021/ic400253m
• 作为产物：
  描述：

  C₈H₆S₈^(2-)*2Na⁽¹⁺⁾ 、 2-(氯甲基)-1-氧代吡啶-1-鎓 以 乙醇 为溶剂， 反应 16.0h， 以360 mg的产率得到[4,5-bis(2-pyridyl-N-oxidemethylthio)]-4′,5′-methyldithiotetrathiafulvalene
  参考文献：
  名称：

  A Series of Tetrathiafulvalene-Based Lanthanide Complexes Displaying Either Single Molecule Magnet or Luminescence—Direct Magnetic and Photo-Physical Correlations in the Ytterbium Analogue

  摘要：

  The reaction between (4,5-bis(2-pyridyl-N-oxidemethylthio)-4',5')-ethylenedithiotetrathiafulvene (L-1) or -methyldithiotetrathiafulvene (L-2) ligands and Ln(hfac)(3)center dot nH(2)O precursors (Ln(III) = Pr, Tb, Dy, Er, and Yb) leads to the formation of seven dinudear complexes of formula [Ln(2)(hfac)(6)(H2O)(x)(L-y)(2)] (x = 2 and y = 1 for L-III = Pr (1); x = 0 and y = 1 for Ln(III) = Tb (2), Dy (3), Er (4) and Yb (5); x = 0 and y = 2 for Ln(III) = Tb (6) and Dy (7)). Their X-ray structures reveal that the coordination environment of each Ln(III) center is filled by two N-oxide groups coming from two different ligands L-y. UV-visible absorption properties have been experimentally measured and rationalized by TD-DFT calculations. The temperature dependences of static magnetic measurements have been fitted. The ground state corresponds to the almost pure vertical bar M-J = +/- 13/2 > while the first excited state (+/- 0.77 vertical bar +/- 11/2 > +/- 0.50 vertical bar +/- 3/2 > +/- 0.39 vertical bar +/- 5/2 >) is located at 19 cm(-1) and 26.9 cm(-1) respectively for 3 and 7. Upon irradiation at 77 K and at room temperature, in the range 25 000-20 835 cm(-1), both compounds 4 and 5 display a metal-centered luminescence attributed to I-4(13/2) -> I-4(15/2) (6660 cm(-1)) and F-2(5/2) -> E-2(7/2) (9972 cm(-1)) transitions, respectively. Emission spectroscopy provides a direct probe of the vertical bar +/- 5/2 > ground state multiplet splitting, which has been confronted to magnetic data. The energy separation of 225 cm(-1) between the ground state and the first excited level (M-J = +/- 3/2) fits exactly the second emission line (234 cm(-1)). While no out-phase-signal is detected for 3, the change of ligand L-1 -> L-2 induces a change of coordination sphere symmetry around the Dy-III increasing the energy splitting between the ground and first excited states, and 7 displays a single molecule magnet behavior.

  DOI：

  10.1021/ic400253m

文献信息

• Difluorodioxophosphate-Based Hollow Hexanuclear Lanthanide(III) Clusters Decorated with Tetrathiafulvalene Ligands
  作者：Tamyris T. da Cunha、Fabrice Pointillart、Boris Le Guennic、Cynthia L. M. Pereira、Stéphane Golhen、Olivier Cador、Lahcène Ouahab

  DOI：10.1021/ic4012839

  日期：2013.9.3

  The galvanostatic reaction of the [4,5-bis(2-pyridyl-N-oxidemethylthio)]-4',5'-methyldithiotetrathia fulvalene ligand with lanthanide ions in the presence of hexafluorophosphate (PF6-) anions afforded the highest-nuclearity lanthanide clusters decorated by tetrathiafulva, lene-based ligands thanks to the original partial hydrolysis of the PF6- anions in difluorodioxophosphate (PO2F2-) bridging ligands.