methyl 5-(diphenyloxophosphino)-2,2'-bithiophene-5'-carboxylate | 1374873-33-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 双噻吩和低聚噻吩
• 英文名称: methyl 5-(diphenyloxophosphino)-2,2'-bithiophene-5'-carboxylate
• 英文别名: Methyl 5-(5-diphenylphosphorylthiophen-2-yl)thiophene-2-carboxylate；methyl 5-(5-diphenylphosphorylthiophen-2-yl)thiophene-2-carboxylate
• CAS: 1374873-33-2
• 化学式: C₂₂H₁₇O₃PS₂
• 分子量: 424.481
• InChiKey: PVTFEANMJMASDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  99.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2,2'-联二噻吩 在 sodium tetrahydroborate 、 正丁基锂 、 双氧水 、 碘 、 potassium carbonate 、 三氯氧磷 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 1,2-二氯乙烷 、 丙酮 为溶剂， 反应 56.83h， 生成 methyl 5-(diphenyloxophosphino)-2,2'-bithiophene-5'-carboxylate
  参考文献：
  名称：

  Syntheses, X-ray Crystal Structures, and Optical, Fluorescence, and Nonlinear Optical Characterizations of Diphenylphosphino-Substituted Bithiophenes

  摘要：

  A series of bithiophene derivatives that are either symmetrically disubstituted with two Ph-2(X)P groups (X = O, S, Se) or monosubstituted with one Ph-2(X)P group (X = O, S, Se) and an organic functional group (H, CHO, CH2OH, CO2Me) have been synthesized. The X-ray crystal structures of Ph-2(Se)P(C4H2S)(2)P(Se)Ph-2, Ph-2(O)P(C4H2S)(2)H, Ph-2(S)P(C4H2S)(2)H, and Ph-2(O)P(C4H2S)(2)CH2OH exhibit very different solid-state structures depending on the type of intermolecular pi-pi interactions that occur. The compounds have been characterized by electronic absorption and fluorescence studies. Of particular interest is that the quantum yields of Ph-2(O)P(C4H2S)(2)H, Ph-2(O)P(C4H2S)(2)P(O)Ph-2, Ph-2(O)P(C4H2S)(2)CO2Me, and Ph-2(O)P(C4H2S)(2)CH2OH are significantly larger than that of bithiophene (factors of 13, 14, 14, and 2,2, respectively). This behavior is quite different from that of analogously substituted terthiophenes in which substitution results in only modest increases in the quantum yields over that of terthiophene (factors of 0.94, 2.7, 1.3, and 1.5, respectively). DFT studies of the emission process suggest that modifying the Ph-2(X)P group affects both the fluorescence and nonradiative rate constants while modifications of the organic substituents primarily affect the nonradiative rate constants. The higher quantum yields of the substituted bithiophenes make them promising for application in organic light-emitting devices (OLED). The optical power limiting (OPL) performances of these Ph-2(X)P-substituted bithiophenes were evaluated by nonlinear transmission measurements in the violet-blue spectral region (430-480 nm) with picosecond laser pulses. The OPL performances are enhanced by heavier X groups and when by higher solubilities. Saturated chloroform solutions of Ph-2(O)P(C4H2S)(2)H and Ph-2(S)P(C4H2S)(2)H exhibit significantly stronger nonlinear absorption than any previously reported compounds and are promising candidates for use in broadband optical power limiters.

  DOI：

  10.1021/ic201309k

文献信息

• Syntheses, X-ray Crystal Structures, and Optical, Fluorescence, and Nonlinear Optical Characterizations of Diphenylphosphino-Substituted Bithiophenes
  作者：Qun Zhao、Jason L. Freeman、Jianwei Wang、Yuanli Zhang、Tracy P. Hamilton、Christopher M. Lawson、Gary M. Gray

  DOI：10.1021/ic201309k

  日期：2012.2.20

  A series of bithiophene derivatives that are either symmetrically disubstituted with two Ph-2(X)P groups (X = O, S, Se) or monosubstituted with one Ph-2(X)P group (X = O, S, Se) and an organic functional group (H, CHO, CH2OH, CO2Me) have been synthesized. The X-ray crystal structures of Ph-2(Se)P(C4H2S)(2)P(Se)Ph-2, Ph-2(O)P(C4H2S)(2)H, Ph-2(S)P(C4H2S)(2)H, and Ph-2(O)P(C4H2S)(2)CH2OH exhibit very different solid-state structures depending on the type of intermolecular pi-pi interactions that occur. The compounds have been characterized by electronic absorption and fluorescence studies. Of particular interest is that the quantum yields of Ph-2(O)P(C4H2S)(2)H, Ph-2(O)P(C4H2S)(2)P(O)Ph-2, Ph-2(O)P(C4H2S)(2)CO2Me, and Ph-2(O)P(C4H2S)(2)CH2OH are significantly larger than that of bithiophene (factors of 13, 14, 14, and 2,2, respectively). This behavior is quite different from that of analogously substituted terthiophenes in which substitution results in only modest increases in the quantum yields over that of terthiophene (factors of 0.94, 2.7, 1.3, and 1.5, respectively). DFT studies of the emission process suggest that modifying the Ph-2(X)P group affects both the fluorescence and nonradiative rate constants while modifications of the organic substituents primarily affect the nonradiative rate constants. The higher quantum yields of the substituted bithiophenes make them promising for application in organic light-emitting devices (OLED). The optical power limiting (OPL) performances of these Ph-2(X)P-substituted bithiophenes were evaluated by nonlinear transmission measurements in the violet-blue spectral region (430-480 nm) with picosecond laser pulses. The OPL performances are enhanced by heavier X groups and when by higher solubilities. Saturated chloroform solutions of Ph-2(O)P(C4H2S)(2)H and Ph-2(S)P(C4H2S)(2)H exhibit significantly stronger nonlinear absorption than any previously reported compounds and are promising candidates for use in broadband optical power limiters.