8-chloro-bis[1,2,3]dithiazolo[4,5-b:5‘,4‘-e]pyridine | 289895-20-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 8-chloro-bis[1,2,3]dithiazolo[4,5-b:5‘,4‘-e]pyridine
• 英文别名: 8-chlorobis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridine
• CAS: 289895-20-1
• 化学式: C₅ClN₃S₄
• 分子量: 265.792
• InChiKey: GGJSSKLYCHBLCD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.12
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  39.35
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2,2,2-三氟乙基三氟甲烷磺酸酯 、 8-chloro-bis[1,2,3]dithiazolo[4,5-b:5‘,4‘-e]pyridine 以 1,2-二氯乙烷 为溶剂， 反应 40.0h， 以81%的产率得到8-chloro-4-(2,2,2-trifluoroethyl)-4H-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridin-2-ium triflate
  参考文献：
  名称：

  Ferromagnetic Ordering in Bisthiaselenazolyl Radicals: Variations on a Tetragonal Theme

  摘要：

  A series of five isostructural bisthiaselenazolyl radicals 2 have been prepared and characterized by X-ray crystallography. The crystal structures, all belonging to the tetragonal space group P (4) over bar2(1)m, consist of slipped pi-stack arrays of undimerized radicals packed about (4) over bar centers running along the z-direction, an arrangement which gives rise to a complex lattice-wide network of close intermolecular Se---Se' contacts. Variations in R, (Et, Pr, CH2CF3) with R-2 = Cl lead to significant changes in the degree of slippage of the pi-stacks and hence the proximity of the Se---Se' interactions. By contrast, variations in R-2 (Cl, Br, Me) with R, = Et induce very little change in either the degree of slippage or the intermolecular contacts. Variable-temperature conductivity (sigma) measurements show relatively constant values for the conductivity sigma(300 K) (10(-5)-10(-4) S cm(-1)) and thermal activation energy E-act (0.27-0.31 eV). Variable-temperature magnetic susceptibility measurements indicate that radicals 2b and 2c (R-1 = Pr, CH2CF3; R-2 = Cl) behave as weakly antiferromagnetically coupled Curie-Weiss paramagnets, but in 2a, 2d and 2e (R-1 = Et; R-2 = Cl, Me, Br) ferromagnetic ordering is observed, with T-c values of 12.8 (R-2 = Cl), 13.6 (R-2 = Me), and 14.1 K (R-2 = Br). The origin of the dramatically different magnetic behavior across the series has been explored in terms of a direct through-space mechanism by means of DFT calculations on individual pairwise exchange energies. These indicate that antiferromagnetic exchange between radicals along the g-stacks increases with pi-stack slippage.

  DOI：

  10.1021/ja8054436
• 作为产物：
  描述：

  8-chloro-4H-bis[1,2,3]dithiazolo[4,5:5'4']pyridin-2-ium hexafluoroantimonate 在 Proton Sponge 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.08h， 以98%的产率得到8-chloro-bis[1,2,3]dithiazolo[4,5-b:5‘,4‘-e]pyridine
  参考文献：
  名称：

  Resonance-Stabilized 1,2,3-Dithiazolo-1,2,3-dithiazolyls as Neutral π-Radical Conductors

  摘要：

  Alkylation of the zwitterionic heterocycle 8-chloro-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridine (CIBP) with alkyl triflates affords 8-chloro-4-alkyl-4H-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridin-2-ium triflates [CIBPR]-[OTf] (R = Me, Et, Pr). Reduction of these salts with decamethylferrocene affords the corresponding CIBPR radicals as thermally stable crystalline solids. The radicals have been characterized in solution by cyclic voltammetry and EPR spectroscopy. Measured electrochemical cell potentials and computed (B3LYP/631 G**) gas-phase disproportionation enthalpies are consistent with a low on-site Coulombic barrier U to charge transfer in the solid state. The crystal structures of CIBPR (R = Me, Et, Pr) have been determined by X-ray crystallography (at 293 K). All three structures consist of slipped pi-stacks of undimerized radicals, with many close intermolecular S...S contacts. CIBPMe undergoes a phase transition at 93 K to a slightly modified slipped g-stack arrangement, the structure of which has also been established crystallographically (at 25 K). Variable-temperature magnetic and conductivity measurements have been performed, and the results interpreted in light of extended Huckel band calculations. The room-temperature conductivities of CIBPR systems (sigma(RT) approximate to 10(-5) to 10(-6) S cm(-1)), as well as the weak 1 D ferromagnetism exhibited by CIBPMe, are interpreted in terms of weak intermolecular overlap along the pi-stacks. The latter is caused by slippage of the molecular plates, a feature necessitated by the steric size of the R and Cl groups on the pyridine ring.

  DOI：

  10.1021/ja026118s

文献信息

• Bisdithiazolyl Radical Spin Ladders
  作者：Kristina Lekin、Joanne W. L. Wong、Stephen M. Winter、Aaron Mailman、Paul A. Dube、Richard T. Oakley

  DOI：10.1021/ic302658c

  日期：2013.2.18

  A series of four bisdithiazolyl radicals 1a-d (R-1 = Pr, Bu, Pn, Hx; R-2 = F) has been prepared and characterized by X-ray crystallography. The crystal structure of 1a (R-1 = Pr) belongs to the tetragonal space group P (4) over bar2(1)m and consists of slipped pi-stack arrays of undimerized radicals packed about (4) over bar centers running along the z-direction, an arrangement identical to that found for 1 (R-1 = Et; R-2 = F). With increasing chain length of the R-1 substituent, an isomorphous set 1b-d is generated. All three compounds crystallize in the P2(1)/c space group and consist of pairs of radical pi-stacks locked together by strong intermolecular F center dot center dot center dot S' bridges to create spin ladder arrays. The slipped pi-stack alignment of radicals produces close S center dot center dot center dot S' interactions which serve as the "rungs" of a spin ladder, and the long chain alkyl substituents (R-1) serve as buffers which separate the ladders from each other laterally. Variable temperature magnetic susceptibility measurements indicate that la behaves as an antiferromagnetically coupled Curie-Weiss paramagnet, the behavior of which may be modeled as a weakly coupled AFM chain. Stronger antiferromagnetic coupling is observed in 1b-d, such that the Curie-Weiss fit is no longer applicable. Analysis of the full data range (T = 2-300 K) is consistent with the Johnston strong-leg spin ladder model. The origin of the magnetic behavior across the series has been explored with broken-symmetry Density Functional Theory (DFT) calculations of individual pairwise exchange energies. These confirm that strong antiferromagnetic interactions are present within the ladder "legs" and "rungs", with only very weak magnetic exchange between the ladders.