4,10-Diiodo-7-methyl-7-phenyl-3,11-dithia-7-silatricyclo[6.3.0.02,6]undeca-1(8),2(6),4,9-tetraene | 1231544-41-4

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 4,10-Diiodo-7-methyl-7-phenyl-3,11-dithia-7-silatricyclo[6.3.0.02,6]undeca-1(8),2(6),4,9-tetraene
• CAS: 1231544-41-4
• 化学式: C₁₅H₁₀I₂S₂Si
• 分子量: 536.271
• InChiKey: AGRGWGUFFIFCEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-溴萘 、 4,10-Diiodo-7-methyl-7-phenyl-3,11-dithia-7-silatricyclo[6.3.0.02,6]undeca-1(8),2(6),4,9-tetraene 在 正丁基锂 、 indium(III) chloride 、 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 作用下， 以 正己烷 、 四氢呋喃 、 乙醚 为溶剂， 反应 10.0h， 以57%的产率得到7-Methyl-4,10-dinaphthalen-2-yl-7-phenyl-3,11-dithia-7-silatricyclo[6.3.0.02,6]undeca-1(8),2(6),4,9-tetraene
  参考文献：
  名称：

  Palladium-Catalyzed Cross-Coupling Reactions of Dithienosilole with Indium Reagents: Synthesis and Characterization of Dithienosilole Derivatives and Their Application to Organic Light-Emitting Diodes

  摘要：

  Three dithienosilole (DTS) derivatives bearing naphthyl segments, 5,5'-dinaphthyl-1,1-dimethyldithienosilol (1), 5,5'-dinaphthyl-l-methyl-l-phenyldithienosilole (2), and 5,5'-dinaphthyl-1,1-diphenyldithienosilol (3), are prepared through Pd(II)-catalyzed cross-coupling using an organoindium reagent as a nucleophile. The molecular structure of 3 is confirmed by single-crystal X-ray analysis. In addition, thermal, photophysical, and electrochemical properties for all three compounds are systematically investigated. The introduction of naphthyl segments into the DTS framework leads to an excellent enhancement of thermal stability with relatively high glass transition (T(g): 87 degrees C) and decomposition temperatures (T(d): 320-380 degrees C). A red shift in both absorption and emission is observed in the DTS series as the 1,1-substituents on the ring silicon atom become more electronegative. On the basis of absorption spectra and DFT/TDDFT calculations, intense green photoluminescence observed for all compounds can be attributed to the effective pi-pi* transition of the DTS and naphthyl group with a small contribution of the sigma* orbital of the exocyclic Si-C bond. The electron-transporting properties of 1, 2, and 3 were evaluated by the performance of organic light-emitting diodes (OLEDs), comprising 4,4',4 ''-tris(N-(2-naphthyl)-N-phenylamino)triphenylamine (2-TNA-TA) as hole-injection layer, 4,4'-bis(N-phenyl-1-naphthylamino)biphenyl (NPB) as hole-transport layer, 10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-benzo[l]pyrano[678-ij]quinolizin]-11-one(C545T)/tris(8-quinolinato)aluminum (Alq(3)) as emitting layer, and the DTS series as electron-transporting layer, respectively. The device shows intense green emission with a high efficiency of 8.0 cd/A at 1000 cd/m(2).

  DOI：

  10.1021/om100222b
• 作为产物：
  描述：

  4-methyl-4-phenyl-2,6-bis(trimethylsilyl)-4H-silolo[3,2-b:4,5-b']dithiophene 在 一氯化碘 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 6.0h， 以67%的产率得到4,10-Diiodo-7-methyl-7-phenyl-3,11-dithia-7-silatricyclo[6.3.0.02,6]undeca-1(8),2(6),4,9-tetraene
  参考文献：
  名称：

  Palladium-Catalyzed Cross-Coupling Reactions of Dithienosilole with Indium Reagents: Synthesis and Characterization of Dithienosilole Derivatives and Their Application to Organic Light-Emitting Diodes

  摘要：

  Three dithienosilole (DTS) derivatives bearing naphthyl segments, 5,5'-dinaphthyl-1,1-dimethyldithienosilol (1), 5,5'-dinaphthyl-l-methyl-l-phenyldithienosilole (2), and 5,5'-dinaphthyl-1,1-diphenyldithienosilol (3), are prepared through Pd(II)-catalyzed cross-coupling using an organoindium reagent as a nucleophile. The molecular structure of 3 is confirmed by single-crystal X-ray analysis. In addition, thermal, photophysical, and electrochemical properties for all three compounds are systematically investigated. The introduction of naphthyl segments into the DTS framework leads to an excellent enhancement of thermal stability with relatively high glass transition (T(g): 87 degrees C) and decomposition temperatures (T(d): 320-380 degrees C). A red shift in both absorption and emission is observed in the DTS series as the 1,1-substituents on the ring silicon atom become more electronegative. On the basis of absorption spectra and DFT/TDDFT calculations, intense green photoluminescence observed for all compounds can be attributed to the effective pi-pi* transition of the DTS and naphthyl group with a small contribution of the sigma* orbital of the exocyclic Si-C bond. The electron-transporting properties of 1, 2, and 3 were evaluated by the performance of organic light-emitting diodes (OLEDs), comprising 4,4',4 ''-tris(N-(2-naphthyl)-N-phenylamino)triphenylamine (2-TNA-TA) as hole-injection layer, 4,4'-bis(N-phenyl-1-naphthylamino)biphenyl (NPB) as hole-transport layer, 10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-benzo[l]pyrano[678-ij]quinolizin]-11-one(C545T)/tris(8-quinolinato)aluminum (Alq(3)) as emitting layer, and the DTS series as electron-transporting layer, respectively. The device shows intense green emission with a high efficiency of 8.0 cd/A at 1000 cd/m(2).

  DOI：

  10.1021/om100222b

文献信息

• Synthesis and characterization of fluorene and carbazole dithienosilole derivatives for potential applications in organic light-emitting diodes
  作者：Hyoungkeun Park、Yingli Rao、Maria Varlan、Jinho Kim、Soo-Byung Ko、Suning Wang、Youngjin Kang

  DOI：10.1016/j.tet.2012.08.056

  日期：2012.11

  Several fluorene or carbazole-based dithienosiloles (DTSs) have been synthesized and their thermal, photophysical, and electrochemical properties have been systematically investigated. These compounds show high thermal stability with glass transition temperature above 110 degrees C as well as decomposition temperatures at similar to 400 degrees C. Intense green emission is observed in the spectral region of 500-510 nm for all compounds (Phi(PL)=0.31-0.80), that is, attributed to both the 5,5 '-substituents of the DTS ring and DTS-based pi-pi* transition. Based on the emission spectra at 77 K, the triplet energy for these compounds was calculated to be within 2.1-2.2 eV, indicating that they may be used as host materials for red emitters in organic light-emitting diodes (OLEDs). All compounds exhibit reversible oxidation and possess low-lying LUMO energies, owing to the conjugated fluorene/carbazole substituents on the DTS. This along with the high thermal/electrochemical stabilities and high fluorescent quantum efficiencies makes the new DTSs compounds promising candidates for use in OLEDs as emitters, host and electron-transporting materials. (C) 2012 Elsevier Ltd. All rights reserved.