5-(bis(4-methoxyphenyl)amino)thiophene-2-carbaldehyde | 866327-15-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5-(bis(4-methoxyphenyl)amino)thiophene-2-carbaldehyde
• 英文别名: 5-(Bis(4-methoxyphenyl)amino)thiophene-2-carbaldehyde；5-(4-methoxy-N-(4-methoxyphenyl)anilino)thiophene-2-carbaldehyde
• CAS: 866327-15-3
• 化学式: C₁₉H₁₇NO₃S
• 分子量: 339.415
• InChiKey: LSXPQSLJMFAOEG-UHFFFAOYSA-N

物化性质

• 沸点：
  512.7±50.0 °C(Predicted)
• 密度：
  1.258±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  67
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-(bis(4-methoxyphenyl)amino)thiophene-2-carbaldehyde 在 三叔丁基膦 、 potassium tert-butylate 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 sodium t-butanolate 作用下， 以 乙醇 、 甲苯 为溶剂， 生成 9-((5-(bis(4-methoxyphenyl)amino)thiophen-2-yl)methylene)-N2,N2,N7,N7-tetrakis(4-methoxyphenyl)-9H-fluorene-2,7-diamine
  参考文献：
  名称：

  通过分子骨架设计控制多维芳胺基混合价化合物中的电子转移过程

  摘要：

  合成了四种具有三个二芳胺氧化还原中心和二苯并富烯作为核心桥的三角拓扑化合物。它们的自由基阳离子在三个氧化还原中心之间表现出吸引人的分子内电子转移途径，这取决于它们在核心桥上的位置。通过改变这些位置（在 2,7- 或 3,6- 上）和桥的长度，通过电子自交换途径实现了对分子内电子转移途径的控制。通过吸收光谱、电子顺磁共振光谱和（时间相关）密度泛函理论计算研究了这些过程。还进行了空穴迁移率测量，以将分子内电子转移与光电器件中可能应用的空穴传输能力相关联。

  DOI：

  10.1021/acs.jpca.1c05435
• 作为产物：
  描述：

  4,4'-二甲氧基二苯胺 在 tris-(dibenzylideneacetone)dipalladium(0) 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 N,N-二甲基甲酰胺 、 sodium t-butanolate 、 三氯氧磷 作用下， 以 甲苯 为溶剂， 反应 30.0h， 生成 5-(bis(4-methoxyphenyl)amino)thiophene-2-carbaldehyde
  参考文献：
  名称：

  用于倒置钙钛矿太阳能电池的绿色溶剂可加工无掺杂剂空穴传输材料

  摘要：

  具有 3,5-二腈吡啶核的星形供体-受体-供体结构已被开发为一种高效的设计策略，可用于高性能绿色溶剂可加工的无掺杂剂空穴传输材料 (HTM)。由绿色溶剂 2-甲基茴香醚（一种食品添加剂）处理得到的 BTP1 HTM，基于倒置钙钛矿太阳能电池显示出令人印象深刻的 24.34% 的效率。

  DOI：

  10.1002/anie.202218752

文献信息

• Design and synthesis of Phenylaminothiophene donor-based chromophore with enhanced electro-optic activity
  作者：Minfeng Yang、Meishan Peng、Ziheng Li、Ziwei Wang、Fenggang Liu、Weijie Liu、Juanfei Liao、Tongyu Luo、Jiahai Wang

  DOI：10.1016/j.dyepig.2021.109423

  日期：2021.8

  Three novel chromophores B-D have been synthesized based on thiophene derivatived donors, including 5-(methyl(phenyl)amino)thiophene 5-(bis(4-methoxyphenyl)amino)thiophene 5-((4-methoxyphenyl)(methyl)amino)thiophene groups respectively, with the same isophorone-derived bridge and tricyanovinyldihydrofuran (TCF) acceptors. A new strategy was proposed to improve the electron donating ability of the chromophore

  基于噻吩衍生的供体已经合成了三种新型发色团B - D，包括5-（甲基（苯基）氨基）噻吩5-（双（4-甲氧基苯基）氨基）噻吩5-（（4-甲氧基苯基）（甲基）氨基）噻吩基团，具有相同的异佛尔酮衍生桥和三氰基乙烯基二氢呋喃（TCF）受体。提出了改善生色团的电子给体能力的新策略，并探索了噻吩基取代生色团供体部分中的苯基单元。密度泛函理论计算表明，含（芳基氨基）噻吩供体的生色团B - D的第一超极化率比4-（二烷基氨基）苯基对应的生色团高约20％。一。随着供体亚基从烷基苯胺变为（芳氨基）噻吩供体，本体非线性度（r 33）至少提高了50％。掺杂了25％（重量）生色团B - D的聚合物薄膜已经极化，在1.31μm处分别具有131、143和138 pm / V的大r 33值，这远高于生色团A的EO活性（88 pm）。 / V）。
• Miniaturization of molecular conjugated systems for organic solar cells: towards pigmy donors
  作者：Victorien Jeux、Dora Demeter、Philippe Leriche、Jean Roncali

  DOI：10.1039/c3ra40966j

  日期：——

  Organic solar cells with short-circuit current densities and conversion efficiencies of ca. 7.0 mA cm−2 and 2.0%, respectively, have been fabricated with a very small molecular donor based on substituted triarylamines.

  利用一种基于取代三芳基胺的极小分子供体，制造出了短路电流密度和转换效率分别约为 7.0 mA cm-2 和 2.0% 的有机太阳能电池。
• 10.1016/j.dyepig.2023.111410
  作者：Zhang, Lian、Zeng, Ziying、Wu, Shuangke、Luo, Tongyu、Li, Zhibei、Zhang, Weijun、Wu, Weimin、Liu, Haohuai、Liu, Fengang

  DOI：10.1016/j.dyepig.2023.111410

  日期：——

  nonlinear optical chromophores 1–12 were developed based on twelve different types of electron donors, with the same isophorone based bridge and TCF acceptor. The donors studied include Ethyl methylaniline, tetrahydroquinoline, Ethoxykowloon aniline, triphenylamine, thiophen-2-amine derivatives, bis(alkyl)aniline derivatives and poly heteroatom aniline. Thermal stability analysis, optical properties, Density

  不同种类供体的开发和比较在有机功能材料领域显示出非常重要的作用。基于十二种不同类型的电子供体开发了一系列非线性光学发色团 1-12，具有相同的基于异佛尔酮的桥和 TCF 受体。研究的供体包括乙基甲基苯胺、四氢喹啉、乙氧基九龙苯胺、三苯胺、噻吩-2-胺衍生物、双（烷基）苯胺衍生物和聚杂原子苯胺。系统地研究了这些发色团的热稳定性分析、光学性质、密度泛函理论计算（DFT）和电光系数测试，以展示不同供体对发色团性质的影响。结果表明，引入一个或多个杂原子可以有效提高供体的给电子能力，从而提高生色团的第一超极化率。含有 25 wt% 发色团 1-12 的掺杂薄膜显示电光系数分别为 54 到 163 pm/V。
• Boosted electro-optic performance in second-order nonlinear optical chromophores featuring thiophen-2-amine-derived donor groups
  作者：Abdul Rahman、Weijun Zhang、Shuhui Bo、Amjad Ali、Rizwan Wahab、Khurram Shehzad、Fenggang Liu

  DOI：10.1016/j.dyepig.2024.112379

  日期：2024.12

  Two innovative second-order nonlinear optical chromophores, designated as B–C, have been synthesized, featuring thiophene-derived donors and a tricyanovinyldihydrofuran bridge as acceptors. These chromophores have undergone comprehensive characterization. Notably, the donor components of chromophores B–C were (methyl(phenyl)amino)thiophene and (4-methoxyphenylamino)thiophene, respectively, in contrast

  已经合成了两种创新的二阶非线性光学发色团，称为 B-C，其特征是噻吩衍生的供体和三氰基乙烯基二氢呋喃桥作为受体。这些发色团已经过全面的表征。值得注意的是，发色团 B–C 的供体成分分别是（甲基（苯基）氨基）噻吩和（4-甲氧基苯氨基）噻吩，与发色团 A 中存在的二乙氨基苯基单元相反。密度泛函理论计算表明，第一个超极化率具有（甲氧基苯基氨基）噻吩供体的发色团C的电子给电子能力比发色团A和B高约60％。这表明仅用噻吩取代苯环并不能显着增强供体的给电子能力。掺杂有 25 wt% 发色团 AC 的聚合物薄膜的 r33 值分别为 39 pm/V、46 pm/V 和 76 pm/V。发色团B和C的电光系数分别比发色团A高18%和95%。这些发现证实，噻吩衍生的供体，特别是具有多个杂原子的供体，可以有效增强发色团的电光系数。
• Rational Enhancement of Second-Order Nonlinearity: Bis-(4-methoxyphenyl)<i>hetero</i>-aryl-amino Donor-Based Chromophores: Design, Synthesis, and Electrooptic Activity
  作者：Joshua A. Davies、Arumugasamy Elangovan、Philip A. Sullivan、Benjamin C. Olbricht、Denise H. Bale、Todd R. Ewy、Christine M. Isborn、Bruce E. Eichinger、Bruce H. Robinson、Philip J. Reid、Xiaosong Li、Larry R. Dalton

  DOI：10.1021/ja8007424

  日期：2008.8.13

  Two new highly hyperpolarizable chromophores, based on NN-bis-(4-methoxyphenyl)aryl-amino donors and phenyl-trifluoromethyl-tricyanofuran (CF3-Ph-TCF) acceptor linked together via pi-conjugation through 2,5-divinylenethienyl moieties as the bridge, have been designed and synthesized successfully for the first time. The aryl moieties on the donor side of the chromophore molecules were varied as to be thiophene and 1-n-hexylpyrrole. The linear and nonlinear optical (NLO) properties of all compounds were evaluated in addition to recording relevant thermal and electrochemical data. The properties of the two new molecules were comparatively studied. These results are critically analyzed along with two other compounds, reported earlier from our laboratories and our collaborator's, that contain (i) aliphatic chain-bearing aniline and (ii) dianisylaniline as donors, keeping the bridge (2,5-divinylenethienyl-), and the acceptor (CF3-Ph-TCF), constant. Trends in theoretically (density functional theory, DFT) predicted, zero-frequency gas-phase hyperpolarizability [beta(0;0,0)] values are shown to be consistent with the trends in beta HRS(-2 omega;omega,omega), as measured by Hyper-Rayleigh Scattering (HRS), when corrected to zero-frequency using the two-level model (TLM) approximation. Similarly, trends in poling efficiency data (r(33)/E-p) and wavelength dispersion measured by reflection ellipsometry (using a Teng-Man apparatus) and attenuated total reflection (ATR) are found to fit the TLM and DFT predictions. A fold enhancement in bulk nonlinearity (r(33)) is realized as the donor subunits are changed from alkylaniline to dianisylaminopyrrole donors. The results of these studies provide insight into the complicated effects on molecular hyperpolarizability of substituting heteroaromatic subunits into the donor group structures. These studies also demonstrate that, when frequency dependence and electric-field-induced ordering behavior are correctly accounted for, ab initio DFT generated beta(0;0,0) is effective as a predictor of changes in r33 behavior based on chromophore structure modification. Thus DFT can provide valuable insight into the electronic structure origin of complex optical phenomena in organic media.