2,2,6,6-tetra-n-butylbenzo[1,2-d;4,5-d']bis[1,3]dithiole | 1225230-41-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: 2,2,6,6-tetra-n-butylbenzo[1,2-d;4,5-d']bis[1,3]dithiole
• CAS: 1225230-41-0
• 化学式: C₂₄H₃₈S₄
• 分子量: 454.83
• InChiKey: ROTIIRRVUVCRAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.24
• 重原子数：
  28.0
• 可旋转键数：
  12.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  三甲基氯硅烷 、 2,2,6,6-tetra-n-butylbenzo[1,2-d;4,5-d']bis[1,3]dithiole 在 2,2,6,6-四甲基哌啶 、 正丁基锂 、 三乙胺盐酸盐 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  Conjugated Polymers That Respond to Oxidation with Increased Emission

  摘要：

  Thioether-containing poly(para-phenylene-ethynylene) (PPE) copolymers show a strong fluorescence turn-on response when exposed to oxidants in solution as a result of the selective conversion of thioether substituents into sulfoxides and sulfones. We propose that the increase in fluorescence quantum yield (Phi(F)) upon oxidation is the result of both an increase in the rate of fluorescence (k(F)), as a result of greater spatial overlap of the frontier molecular orbitals in the oxidized materials, and an increase in the fluorescence lifetime (tau(F)), due to a decrease in the rate of nonradiative decay. Contrary to established literature, the reported sulfoxides do not always act as fluorescence quenchers. The oxidation is accompanied by spectral changes in the absorption and emission of the polymers, which are dramatic when oxidation causes the copolymer to acquire a donor-acceptor interaction. The oxidized polymers have high fluorescence quantum yields in the solid state, with some having increased photostability. A turn-on fluorescence response to hydrogen peroxide in organic solvents in the presence of an oxidation catalyst indicates the potential of thioether-containing materials for oxidant sensing. The reported polymers show promise as new materials in applications where photostability is important, where tunability of emission across the visible spectrum is desired, and where efficient emission is an advantage.

  DOI：

  10.1021/ja1019063
• 作为产物：
  描述：

  5-壬酮 、 1,2,4,5-四(叔丁硫基)苯 在 四氟硼酸-二乙醚络合物 作用下， 以 甲苯 为溶剂， 以80%的产率得到2,2,6,6-tetra-n-butylbenzo[1,2-d;4,5-d']bis[1,3]dithiole
  参考文献：
  名称：

  Conjugated Polymers That Respond to Oxidation with Increased Emission

  摘要：

  Thioether-containing poly(para-phenylene-ethynylene) (PPE) copolymers show a strong fluorescence turn-on response when exposed to oxidants in solution as a result of the selective conversion of thioether substituents into sulfoxides and sulfones. We propose that the increase in fluorescence quantum yield (Phi(F)) upon oxidation is the result of both an increase in the rate of fluorescence (k(F)), as a result of greater spatial overlap of the frontier molecular orbitals in the oxidized materials, and an increase in the fluorescence lifetime (tau(F)), due to a decrease in the rate of nonradiative decay. Contrary to established literature, the reported sulfoxides do not always act as fluorescence quenchers. The oxidation is accompanied by spectral changes in the absorption and emission of the polymers, which are dramatic when oxidation causes the copolymer to acquire a donor-acceptor interaction. The oxidized polymers have high fluorescence quantum yields in the solid state, with some having increased photostability. A turn-on fluorescence response to hydrogen peroxide in organic solvents in the presence of an oxidation catalyst indicates the potential of thioether-containing materials for oxidant sensing. The reported polymers show promise as new materials in applications where photostability is important, where tunability of emission across the visible spectrum is desired, and where efficient emission is an advantage.

  DOI：

  10.1021/ja1019063

文献信息

• Room-Temperature Electron Spin Relaxation of Triarylmethyl Radicals at the X- and Q-Bands
  作者：Andrey A. Kuzhelev、Dmitry V. Trukhin、Olesya A. Krumkacheva、Rodion K. Strizhakov、Olga Yu. Rogozhnikova、Tatiana I. Troitskaya、Matvey V. Fedin、Victor M. Tormyshev、Elena G. Bagryanskaya

  DOI：10.1021/acs.jpcb.5b03027

  日期：2015.10.29

  Triarylmethyl radicals (trityls, TAMs) represent a relatively new class of spin labels. The long relaxation of trityls at room temperature in liquid solutions makes them a promising alternative for traditional nitroxides. In this work we have synthesized a series of TAMs including perdeuterated Finland trityl (D-36 form), mono-, di-, and triester derivatives of Finland-D-36 trityl, the deuterated form of OX63, the dodeca-n-butyl homologue of Finland trityl, and triamide derivatives of Finland trityl with primary and secondary amines attached. We have studied room-temperature relaxation properties of these TAMs in liquids using pulsed electron paramagnetic resonance (EPR) at two microwave frequency bands. We have found the clear dependence of phase memory time (T-m similar to T-2) on the magnetic field: room-temperature T-m values are similar to 1.5-2.5 times smaller at the Q-band (34 GHz, 1.2 T) than at the X-band (9 GHz, 0.3 T). This trend is ascribed to the contribution from g-anisotropy that is negligible at lower magnetic fields but comes into play at the Q-band. In agreement with this, the difference between T-1 and T-m becomes more pronounced at the Q-band than at the X-band due to increased contributions from incomplete motional averaging of g-anisotropy. Linear dependence of (1/T-m - 1/T-1) on viscosity implies that g-anisotropy is modulated by rotational motion of the trityl radical. On the basis of the analysis of previous data and results of the present work, we conclude that, in the general situation where the spin label is at least partly mobile, the X-band is most suitable for application of trityls for room-temperature pulsed EPR distance measurements.