diethyl (4-bromo-2-thienylmethyl)phosphonate | 224958-14-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl (4-bromo-2-thienylmethyl)phosphonate
• 英文别名: Diethyl [(4-bromothiophen-2-yl)methyl]phosphonate；4-bromo-2-(diethoxyphosphorylmethyl)thiophene
• CAS: 224958-14-9
• 化学式: C₉H₁₄BrO₃PS
• 分子量: 313.152
• InChiKey: NEQGHCRHNJDKBW-UHFFFAOYSA-N

物化性质

• 沸点：
  190 °C(Press: 15 Torr)
• 密度：
  1.461±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  63.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl (4-bromo-2-thienylmethyl)phosphonate 在 sodium hydroxide 、 sodium tetrahydroborate 、 正丁基锂 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 为溶剂， 反应 14.09h， 生成 {5-[2-(4-{[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-methyl-amino}-phenyl)-vinyl]-thiophen-3-yl}-methanol
  参考文献：
  名称：

  Theory-Guided Design and Synthesis of Multichromophore Dendrimers:  An Analysis of the Electro-optic Effect

  摘要：

  Extensive experimental and theoretical study suggests that interchromophore electrostatic interactions are among the most severe impediments to the induction and stability of large electro-optic coefficients in electric-field-poled organic materials. In this report, multichromophore-containing dendritic materials have been investigated as a means to minimize unwanted attenuation of nonlinear optical (electro-optic) activity at high chromophore loading. The dendritic molecular architectures employed were designed to provide optimized molecular scaffolding for electric-field-induced molecular reorientation. Design parameters were based upon past experimental results in conjunction with statistical and quantum mechanical modeling. The electro-optic behavior of these materials was evaluated through experimental and theoretical analysis. Experimental data collected from the dendrimer structures depict a reasonably linear relationship between chromophore number density (N) and electro-optic activity (r(33)) demonstrating a deviation from the dipolar frustration that typically limits r(33) in conventional chromophore/polymer composite materials. The observed linear dependence holds at higher chromophore densities than those that have been found to be practical in systems of organic NLO chromophores dispersed in polymer hosts. Theoretical analysis of these results using Monte Carlo modeling reproduces the experimentally observed trends confirming linear dependence of electro-optic activity on N in the dendrimer materials. These results provide new insight into the ordering behavior of EO dendrimers and demonstrate that the frequently observed asymptotic dependence of electro-optic activity on chromophore number density may be overcome through rational design.

  DOI：

  10.1021/ja068322b
• 作为产物：
  描述：

  (4-溴-2-噻吩基)甲醇 在 盐酸 作用下， 反应 38.0h， 生成 diethyl (4-bromo-2-thienylmethyl)phosphonate
  参考文献：
  名称：

  Theory-Guided Design and Synthesis of Multichromophore Dendrimers:  An Analysis of the Electro-optic Effect

  摘要：

  Extensive experimental and theoretical study suggests that interchromophore electrostatic interactions are among the most severe impediments to the induction and stability of large electro-optic coefficients in electric-field-poled organic materials. In this report, multichromophore-containing dendritic materials have been investigated as a means to minimize unwanted attenuation of nonlinear optical (electro-optic) activity at high chromophore loading. The dendritic molecular architectures employed were designed to provide optimized molecular scaffolding for electric-field-induced molecular reorientation. Design parameters were based upon past experimental results in conjunction with statistical and quantum mechanical modeling. The electro-optic behavior of these materials was evaluated through experimental and theoretical analysis. Experimental data collected from the dendrimer structures depict a reasonably linear relationship between chromophore number density (N) and electro-optic activity (r(33)) demonstrating a deviation from the dipolar frustration that typically limits r(33) in conventional chromophore/polymer composite materials. The observed linear dependence holds at higher chromophore densities than those that have been found to be practical in systems of organic NLO chromophores dispersed in polymer hosts. Theoretical analysis of these results using Monte Carlo modeling reproduces the experimentally observed trends confirming linear dependence of electro-optic activity on N in the dendrimer materials. These results provide new insight into the ordering behavior of EO dendrimers and demonstrate that the frequently observed asymptotic dependence of electro-optic activity on chromophore number density may be overcome through rational design.

  DOI：

  10.1021/ja068322b

文献信息

• FTC-containing molecules: large second-order nonlinear optical performance and excellent thermal stability, and the key development of the “Isolation Chromophore” concept
  作者：Pengyu Chen、Xiuyang Yin、Yujun Xie、Shufang Li、Shiyu Luo、Huiyi Zeng、Guocong Guo、Qianqian Li、Zhen Li

  DOI：10.1039/c6tc04282a

  日期：——

  series of second-order nonlinear optical (NLO) molecules, M1–M5, were designed and successfully synthesized through the convenient ‘‘click chemistry’’ reaction, which contain two different types of chromophore moieties, the FTC chromophore and nitro-based azo ones, according to the concept of “Isolation Chromophore”. All these five molecules possess excellent thermal stability and very large NLO performance

  设计了一系列二阶非线性光学分子（M1-M5），并通过方便的“点击化学”反应成功合成了该分子，其中包含两种不同类型的生色团部分：FTC生色团和基于硝基的偶氮根据“分离发色团”的概念。所有这五个分子均具有出色的热稳定性和非常大的NLO性能，在M1达到的1950 nm波长处具有384 pm V -1的d 33值超高值，进一步促进了优良NLO材料的合理设计。
• A rigid ringlike molecule: large second-order nonlinear optical performance, good temporal and thermal stability, and ideal spherical structure conforming to the “site isolation” principle
  作者：Pengyu Chen、Guangchao Liu、Huanyu Zhang、Meng Jin、Mengmeng Han、Ziyao Cheng、Qian Peng、Qianqian Li、Zhen Li

  DOI：10.1039/c8tc01598h

  日期：——

  molecule of R1, based on the second-order nonlinear optical chromophore of FTC (Fang's Thermally-Stable Chromophore), was designed and synthesized, in which, the heads and waists of two FTC moieties were locked together through chemical bonds, respectively. Thanks to the ideal spherical structure and good alignment of the two pieces of FTC moieties, R1 exhibited an ultra high nonlinear optical effect with

  本文根据位点隔离的原理，设计并合成了基于FTC二阶非线性光学发色团（方氏热稳定发色团）的R1环状分子，其中R1的头和腰两个FTC部分分别通过化学键锁定在一起。由于理想的球形结构和两个FTC部分的良好排列，R1表现出超高的非线性光学效应，在1950 nm波长处的d 33值为562 pm V -1，仍可以在80％的波长下保留80％的光。 145°C的极高温度。
• Theory-Guided Design and Synthesis of Multichromophore Dendrimers:  An Analysis of the Electro-optic Effect
  作者：Philip A. Sullivan、Harrison Rommel、Yi Liao、Benjamin C. Olbricht、Andrew J. P. Akelaitis、Kimberly A. Firestone、Jae-Wook Kang、Jingdong Luo、Joshua A. Davies、Dong Hoon Choi、Bruce E. Eichinger、Philip J. Reid、Antao Chen、Alex K-Y. Jen、Bruce H. Robinson、Larry R. Dalton

  DOI：10.1021/ja068322b

  日期：2007.6.1

  Extensive experimental and theoretical study suggests that interchromophore electrostatic interactions are among the most severe impediments to the induction and stability of large electro-optic coefficients in electric-field-poled organic materials. In this report, multichromophore-containing dendritic materials have been investigated as a means to minimize unwanted attenuation of nonlinear optical (electro-optic) activity at high chromophore loading. The dendritic molecular architectures employed were designed to provide optimized molecular scaffolding for electric-field-induced molecular reorientation. Design parameters were based upon past experimental results in conjunction with statistical and quantum mechanical modeling. The electro-optic behavior of these materials was evaluated through experimental and theoretical analysis. Experimental data collected from the dendrimer structures depict a reasonably linear relationship between chromophore number density (N) and electro-optic activity (r(33)) demonstrating a deviation from the dipolar frustration that typically limits r(33) in conventional chromophore/polymer composite materials. The observed linear dependence holds at higher chromophore densities than those that have been found to be practical in systems of organic NLO chromophores dispersed in polymer hosts. Theoretical analysis of these results using Monte Carlo modeling reproduces the experimentally observed trends confirming linear dependence of electro-optic activity on N in the dendrimer materials. These results provide new insight into the ordering behavior of EO dendrimers and demonstrate that the frequently observed asymptotic dependence of electro-optic activity on chromophore number density may be overcome through rational design.