4-(di(1H-pyrrol-2-yl)methyl)-N,N-diphenylaniline | 1351797-67-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-(di(1H-pyrrol-2-yl)methyl)-N,N-diphenylaniline
• 英文别名: meso-[4-(N,N-diphenylaminophenyl)]dipyrromethane；5-(4-(diphenylamino)phenyl)dipyrromethane；triphenylaminedipyrrane；-
• CAS: 1351797-67-5
• 化学式: C₂₇H₂₃N₃
• 分子量: 389.5
• InChiKey: UXHQTGXMKPXCNV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.99
• 重原子数：
  30.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  34.82
• 氢给体数：
  2.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  4-(di(1H-pyrrol-2-yl)methyl)-N,N-diphenylaniline 在 sodium tetrahydroborate 、 乙基溴化镁 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 19.0h， 生成 (5,5'-((4-(diphenylamino)phenyl)methylene)bis(1H-pyrrole-5,2-diyl))bis((3,5-di-tert-butylphenyl)methanol)
  参考文献：
  名称：

  设计的含电子给体和受主基团的卟啉衍生物的合成及能隙分析

  摘要：

  通过双吡咯2D，2A1-2A5与相应的醛3或二醇6的麦克唐纳偶联，合成了对称的（DD，AA1-AA5）和非对称的（DA1）卟啉衍生物。测量并分析了这些卟啉的UV-Vis光谱和CV的带隙和HOMO-LUMO能量。随着吸电子基团的增加，卟啉PP的带隙增加，而金属卟啉PP-M的带隙减少。PP的HOMO水平和PP-M的LUMO水平比PP的LUMO和PP-M的HOMO低得多， 分别。所有PP和PP–M的LUMO能级均低于P3HT（−2.80 eV），PP和PP–M的所有HOMO能级均高于PCBM（−6.20 eV）。

  DOI：

  10.1002/bkcs.11680
• 作为产物：
  描述：

  三苯胺 在 三氟乙酸 、 三氯氧磷 作用下， 反应 1.0h， 生成 4-(di(1H-pyrrol-2-yl)methyl)-N,N-diphenylaniline
  参考文献：
  名称：

  Triphenylamine-decorated BODIPY fluorescent probe for trace detection of picric acid

  摘要：

  近红外光活性材料TBMA表现出对槲皮酸检测具有高选择性和高灵敏度，检测限低，猝灭常数高。

  DOI：

  10.1039/c5ra12154j

文献信息

• Synthesis and Properties of Novel Borondipyrromethene (BODIPY)-Tethered Triphenylamine Conjugates
  作者：Yucai Wang、Junxu Liao、Bangying Wang、Hongbiao Chen、Hongbin Zhao、Min Peng、Sujuan Fan

  DOI：10.1071/ch15026

  日期：——

  A series of novel donor–acceptor type borondipyrromethene (BODIPY)-tethered triphenylamine conjugates (BDP4–8) containing one or two BODIPY cores attached to a triphenylamine scaffold at the 4- or 4,4′- positions were successfully synthesised via a mild and effective protocol. Their photophysical and electrochemical properties were investigated. The absorption spectra indicated that the meso-substituted BODIPY with triphenylamine did not give rise to an intense intramolecular charge transfer (ICT) and did not effectively extend the conjugated length compared with substitution at the 2,6- and 3,5-positions as previously reported. It is worth noticing that the asymmetric mono-BODIPY-tethered triphenylamine conjugates (BDP5, BDP7) showed an electronic distribution imbalance due to the special 3D propeller shape of triphenylamine resulting in twisted molecular space configurations. In contrast, the symmetric bis-BODIPY-tethered triphenylamine conjugates (BDP4, BDP6, and BDP8) exhibited a balanced electronic distribution. The photoluminescence spectra of these conjugates exhibited significant Stokes shifts (5300–6700 cm–1), which caused fluorescence emission spectra in near-infrared regions. Cyclic voltammograms reveal that the asymmetric mono-BODIPY-tethered triphenylamine conjugates (BDP5, BDP7) have higher LUMO energy levels and lower HOMO energy levels, thus resulting in larger bandgaps than the bis-BODIPY-tethered triphenylamine ones.

  通过一种温和有效的方法，成功合成了一系列新型供体-受体型硼二吡咯并乙烯（BODIPY）-系链三苯胺共轭物（BDP4-8），这些共轭物含有一个或两个 BODIPY 核心，并在 4- 或 4,4′- 位连接到三苯胺支架上。研究了它们的光物理和电化学特性。吸收光谱表明，与之前报道的在 2,6- 位和 3,5- 位取代相比，三苯胺介观取代的 BODIPY 没有产生强烈的分子内电荷转移（ICT），也没有有效地延长共轭长度。值得注意的是，由于三苯胺特殊的三维螺旋桨形状导致分子空间构型扭曲，不对称的单 BODIPY 系三苯胺共轭物（BDP5、BDP7）显示出电子分布不平衡。相比之下，对称的双 BODIPY 系三苯胺共轭物（BDP4、BDP6 和 BDP8）则表现出平衡的电子分布。这些共轭物的光致发光光谱表现出明显的斯托克斯偏移（5300-6700 cm-1），从而导致荧光发射光谱位于近红外区域。循环伏安图显示，不对称的单 BODIPY 系三苯胺共轭物（BDP5 和 BDP7）具有较高的 LUMO 能级和较低的 HOMO 能级，因此比双 BODIPY 系三苯胺共轭物具有更大的带隙。
• BSA-coated fluorescent organic–inorganic hybrid silica nanoparticles: preparation and drug delivery
  作者：Zengming Yang、Hengchang Ma、Zijie Jin、Haiying Cao、Lei Lei、Yucheng Ma、Ziqiang Lei

  DOI：10.1039/c6nj03915d

  日期：——

  A novel BSA-coated inorganic–organic hybrid nano-material with drug delivery ability under stimulation by temperature changes is reported.

  报道了一种新型的BSA包被的无机-有机混合纳米材料，具有在温度变化刺激下的药物输送能力。
• Modulation of energy levels by donor groups: an effective approach for optimizing the efficiency of zinc-porphyrin based solar cells
  作者：Bo Liu、Weihong Zhu、Yueqiang Wang、Wenjun Wu、Xin Li、Baoqin Chen、Yi-Tao Long、Yongshu Xie

  DOI：10.1039/c2jm16804a

  日期：——

  In the design of efficient sensitizers for dye-sensitized solar cells (DSSCs), it is vital to modulate the HOMO and LUMO orbitals by introducing suitable donor and acceptor groups. In this respect, triphenylamine has been extensively used as the donor group. Porphyrin has strong absorption in the UV-Vis range, which makes it a promising dye candidate. In addition, a porphyrin molecule contains eight β positions and four meso-positions, which may be conveniently utilized for introducing multiple donor and acceptor moieties. In this work, various numbers of triphenylamine and trimethoxyphenyl groups are introduced to the porphyrin meso-positions as electron donors, with the aim to systematically modulate the energy levels and investigate the effect on the efficiency of the DSSCs. The HOMO–LUMO energy gaps remain almost constant irrespective of the donor groups, thus, the variation of the donors leads to a contradictory effect on the processes of electron injection and dye regeneration. In the case of the zinc porphyrin with two triphenylamine units and one trimethoxyphenyl group as the electron donors (M3T2P), moderate and well-matched HOMO and LUMO energy levels are observed, thus affording high efficiencies for both the electron injection and the dye regeneration processes. The overall conversion efficiencies (η) of the DSSCs based on these dyes lie in the range of 2.70–5.45%, with the optimized performance achieved by M3T2P, which can be rationalized by the efficient electron injection and dye regeneration processes, and the long electron lifetime, as demonstrated by the electrochemical impedance spectroscopy measurements. These results provide further insights into the strategy for elevating the efficiencies of DSSCs, especially those based on porphyrins, simply by modulating the electron donor groups.

  在设计用于染料敏化太阳能电池（DSSC）的高效敏化剂时，通过引入合适的供体和受体基团来调节 HOMO 和 LUMO 轨道至关重要。在这方面，三苯胺已被广泛用作供体基团。卟啉在紫外可见光范围内有很强的吸收能力，因此是一种很有前途的候选染料。此外，卟啉分子包含 8 个 β 位和 4 个中间位，可方便地用于引入多个供体和受体分子。在这项研究中，卟啉中位引入了不同数量的三苯胺基团和三甲氧基苯基基团作为电子供体，目的是系统地调节能级并研究其对 DSSC 效率的影响。无论供体基团如何，HOMO-LUMO 能隙几乎保持不变，因此，供体的变化会对电子注入和染料再生过程产生相互矛盾的影响。而以两个三苯胺单元和一个三甲氧基苯基为电子供体的卟啉锌（M3T2P），其 HOMO 和 LUMO 能级适中且匹配良好，因此电子注入和染料再生过程的效率都很高。基于这些染料的 DSSC 的总体转换效率（η）介于 2.70% 至 5.45% 之间，其中 M3T2P 实现了最佳性能，这可以通过高效的电子注入和染料再生过程以及较长的电子寿命得到合理解释，电化学阻抗谱测量结果也证明了这一点。这些结果使人们进一步了解了通过调节电子供体基团来提高 DSSC（尤其是基于卟啉的 DSSC）效率的策略。
• Triphenylamine substituted dipyrrinato metal complexes: Synthesis, optical and electrochemical studies
  作者：Sudipta Das、Iti Gupta

  DOI：10.1016/j.inoche.2015.07.019

  日期：2015.10

  Abstract A series of triphenylamine substituted dipyrrinato metal complexes (1–8) have been synthesized. The mononuclear type complexes 1–6 have Ni(II), Co(II), Pd(II), In(III), and Zn(II) metal ions in the core. The binuclear type complexes 7 and 8 have Zn(II) metal ion in the center. All the compounds (1–8) were characterized by HRMS, NMR, IR, UV–vis absorption, cyclic voltammetry and fluorescence

  摘要 合成了一系列三苯胺取代的双吡喃金属络合物 (1-8)。单核型配合物 1-6 在核中具有 Ni(II)、Co(II)、Pd(II)、In(III) 和 Zn(II) 金属离子。双核型配合物7和8在中心具有Zn(II)金属离子。所有化合物 (1-8) 均通过 HRMS、NMR、IR、UV-vis 吸收、循环伏安法和荧光技术进行表征。双吡喃配体上大的富电子三苯胺部分的存在影响了配合物的光谱特性。除了 Co(II) 配合物，其他金属配合物在 UV-vis 研究中表现出蓝移吸收最大值。与相应的苯基类似物相比，In(III) 和 Zn(II) 金属配合物 4-6 在荧光中显示出红移发射最大值。配合物 3-8 在 4600 到 7000 cm-1 范围内表现出良好的斯托克斯位移，同时降低了量子产率。复合物 3-8 的单线态寿命在 2 到 4 ns 范围内；辐射衰减常数 kr 的减少和非辐射衰减常数
• Synthesis and Band Gap Analysis of Meso-Arylporphyrins Containing Exclusively Electron Donating or Withdrawing Groups
  作者：Kang, Min Su、Hwang, Kwang-Jin

  DOI：10.5012/jkcs.2023.67.3.175

  日期：——

  Tetra-aryl substituted A4-type porphyrins (TP, TD, TA) and trans-A2B2 porphyrins (DDP1, AAP1) with electron-donating or withdrawing groups were synthesized. The band gap energy of those porphyrins was calculated from their UV-Vis spectra and CV data. With an electron-withdrawing group, the band gap energy of porphyrin TA increased via the LUMO energy up. Meanwhile, the introduction of an electron-donating group decreased the band gap of porphyrin by HOMO level up as as in the case of porphyrin TD. The band gap (2.19-2.28 eV) of metalloporphyrin PP-Ni was greater than those (1.81-2.06 eV) of non-metalloporphyrins PP due to the LUMO level up.

  合成了具有电子供体或电子受体基团的四芳基取代A4型卟啉（TP、TD、TA）和反式A2B2卟啉（DDP1、AAP1）。根据紫外-可见光谱和CV数据计算了这些卟啉的带隙能量。对于具有电子受体基团的卟啉TA，其带隙能量随着LUMO能级升高而增加。同时，引入电子供体基团使卟啉的带隙随着HOMO能级升高而降低，与卟啉TD的情况相同。由于LUMO能级升高，金属卟啉PP-Ni的带隙（2.19-2.28 eV）大于非金属卟啉PP的带隙（1.81-2.06 eV）。