4-(N,N-bis(4-tert-butylbiphenyl-4'-yl)amino)aniline | 850354-63-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-(N,N-bis(4-tert-butylbiphenyl-4'-yl)amino)aniline
• 英文别名: bis(4'-tert-butylbiphenyl-4-yl)-4-aminophenylamine；4-N,4-N-bis[4-(4-tert-butylphenyl)phenyl]benzene-1,4-diamine
• CAS: 850354-63-1
• 化学式: C₃₈H₄₀N₂
• 分子量: 524.749
• InChiKey: DXUSLVZTSFLBEP-UHFFFAOYSA-N

物化性质

• 熔点：
  87-92 °C
• 沸点：
  673.5±55.0 °C(Predicted)
• 密度：
  1.077±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.1
• 重原子数：
  40
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  29.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(N,N-bis(4-tert-butylbiphenyl-4'-yl)amino)aniline 、 达比加群酯杂质32 在 溶剂黄146 作用下， 反应 48.0h， 以49%的产率得到4-[bis(4'-tert-butylbiphenyl-4-yl)amino]-4'-cyanoazobenzene
  参考文献：
  名称：

  Two-Photon Fluorescent Holographic Rewritable Micropatterning

  摘要：

  Monomeric amorphous systems involving an upper azo-based layer and a lower fluorophore layer have been carefully designed to enable holographic formation of micrometric emissive photopatterns through reversible photoinduced mass migration of azoderivatives. The fluorescent patterns evidenced by NIR biphotonic excitation match the micrometric surface relief. After successful erasure by using a circularly polarized visible light, new patterns can be written again.

  DOI：

  10.1021/ja0735756
• 作为产物：
  描述：

  二(4-溴苯基)胺 在 palladium on activated charcoal 、 四(三苯基膦)钯 sodium carbonate 、 potassium carbonate 、 一水合肼 作用下， 以 甲醇 、 乙醇 、 二甲基亚砜 、 甲苯 为溶剂， 反应 35.0h， 生成 4-(N,N-bis(4-tert-butylbiphenyl-4'-yl)amino)aniline
  参考文献：
  名称：

  Two-Photon Fluorescent Holographic Rewritable Micropatterning

  摘要：

  Monomeric amorphous systems involving an upper azo-based layer and a lower fluorophore layer have been carefully designed to enable holographic formation of micrometric emissive photopatterns through reversible photoinduced mass migration of azoderivatives. The fluorescent patterns evidenced by NIR biphotonic excitation match the micrometric surface relief. After successful erasure by using a circularly polarized visible light, new patterns can be written again.

  DOI：

  10.1021/ja0735756

文献信息

• Decoupling Fluorescence and Photochromism in Bifunctional Azo Derivatives for Bulk Emissive Structures
  作者：Aurélie Jacquart、René M. Williams、Albert M. Brouwer、Eléna Ishow

  DOI：10.1002/chem.201103411

  日期：2012.3.19

  Bifunctional molecules that combine independent push–pull fluorophores and azo photochromes have been synthesized to create fluorescent structures upon light‐induced migration in neat thin films. Their photochromic and emissive properties have been systematically investigated and interpreted in light of those of the corresponding model compounds. Fluorescence lifetimes and photoisomerization and fluorescence

  结合了独立的推挽式荧光团和偶氮光致变色剂的双功能分子已经合成，可以在光诱导下在纯净薄膜中迁移时产生荧光结构。他们的光致变色和发射特性已根据相应的模型化合物进行了系统的研究和解释。在甲苯溶液中已经确定了荧光寿命和光异构化以及荧光量子产率。飞秒瞬态吸收光谱的动力学分析表明，荧光团在数皮秒内演变为扭曲的分子内电荷转移激发态，能量稳定。与偶氮部分的能量转移过程竞争性地发生了辐射弛豫到基态的过程。
• Synthesis of [60]fullerene-functionalized rotaxanes
  作者：Hisahiro Sasabe、Kei-ichiro Ikeshita、G. Abraham Rajkumar、Nobuhiro Watanabe、Nobuhiro Kihara、Yoshio Furusho、Kazuhiko Mizuno、Akiya Ogawa、Toshikazu Takata

  DOI：10.1016/j.tet.2005.09.149

  日期：2006.2

  Synthesis of [60]fullerene (C60)-functionalized rotaxanes via Diels–Alder reactions with C60 is described. Diels–Alder reaction of C60 and sulfolene moiety as masked diene attached on the wheels of rotaxanes results in high yields of C60 incorporation. Rotaxanes are prepared by tin-catalyzed urethane-forming end-capping reaction with isocyanate of pseudorotaxane having the wheel carrying C60 functionality

  描述了通过Diels–Alder与C 60反应合成[60]富勒烯（C 60）-官能化轮烷的方法。Diels-C 60和环戊烷轮子上附着的被掩蔽的二烯所形成的亚砜部分的Diels-Alder反应导致C 60的掺入量很高。轮烷是通过锡催化氨基甲酸酯与端轮烷的异氰酸酯的端基封端反应而制备的，轮烷具有Diels-Alder反应引入的带有C 60官能度的轮子。Diels–Alder反应是通过C 60和假轮烷中带有端基的伪轮烷的端基反应（作为掩蔽的二烯）完成的。各种C 60这些Diels-Alder规程以中等到良好的收率制备了含[2]轮烷的化合物。
• Photoinduced Intramolecular Electron-Transfer Processes in [60]Fullerene-(Spacer)-<i>N,N</i>-Bis(biphenylyl)aniline Dyad in Solutions
  作者：G. Abraham Rajkumar、Atula S. D. Sandanayaka、Kei-ichiro Ikeshita、Mitsunari Itou、Yasuyuki Araki、Yoshio Furusho、Nobuhiro Kihara、Osamu Ito、Toshikazu Takata

  DOI：10.1021/jp046879c

  日期：2005.3.1

  Intramolecular photoinduced charge-separation and charge-recombination processes in a covalently connected C60-(spacer)-N,N-bis(biphenylyl)aniline (C60-spacer-BBA) dyad, in which the center-to-center distance of the electron acceptor and electron donor is 15 A, have been studied by time-resolved fluorescence and transient absorption methods. The observed low fluorescence intensity and the short fluorescence

  共价连接的C60-（间隔基）-N，N-双（联苯基）苯胺（C60-间隔基-BBA）二价分子内的分子内光诱导电荷分离和电荷复合过程，其中电子的中心距受体和电子供体为15 A，已通过时间分辨荧光和瞬态吸收方法进行了研究。在PhCN和THF中观察到的低荧光强度和二元组C60部分的短荧光寿命表明，电荷分离是通过C60部分的激发单重态以非常快的速度和高效率进行的。PhCN和THF中的纳秒瞬态吸收光谱显示在880和1100 nm处有宽吸收带，这归因于C60（*-）-间隔物-BBA（* +）。在室温下，PhCN和THF中电荷分离态的寿命为330-360 ns。根据温度与电荷重组速率常数的关系，重组能量估计为0.77-0.87 eV，这表明电荷重组过程位于抛物线的马库斯区。随着温度降低，由于C60（*-）-间隔基-BBA（* +）溶剂化的增加，经由C60部分的激发三重态的电荷分离贡献增加。
• Syntheses of [60]Fullerene and<i>N,N</i>-Bis(4-biphenyl)aniline-Tethered Rotaxane: Photoinduced Electron-Transfer Processes via Singlet and Triplet States of [60]Fullerene
  作者：Atula S. D. Sandanayaka、Kei-ichiro Ikeshita、Nobuhiro Watanabe、Yasuyuki Araki、Yoshio Furusho、Nobuhiro Kihara、Toshikazu Takata、Osamu Ito

  DOI：10.1246/bcsj.78.1008

  日期：2005.6

  A rotaxane containing [60]fullerene (C60) and N,N-bis(4-biphenyl)aniline (BBA) moieties was synthesized. In this structure, C60 acting as an electron acceptor, is attached to the crown-ether ring through which the axle with terminal BBA moieties acting as electron donors on both ends is penetrating. This rotaxane had a neutral amide moiety in the center of the axle in which two BBA moieties act as stoppers. The intra-rotaxane photoinduced electron-transfer processes of the C60 and BBA moieties were investigated by time-resolved transient absorption and fluorescence measurements while changing solvent polarity and temperature. Time-resolved transient absorption measurements of the rotaxanes confirmed that the long-lived charge-separated state (C60•−; BBA•+)rotaxane was formed via both the excited singlet and triplet states of C60 (1C60* and 3C60*, respectively) in polar solvents. The rate constants for charge-separation process were evaluated to be in the range of (3.6–3.7) × 108 s−1 via 1C60* and (5.1–5.6) × 107 s−1 via 3C60* in the ratio of (0.36–0.38):(0.43–0.51). The rate constants of charge recombination were 2.5 × 106 s−1 and 4.4 × 106 s−1, corresponding to the lifetimes of the charge-separated states of 400 ns and 230 ns in THF and benzonitrile, respectively. By the temperature dependences, the activation free-energy changes of charge-separation process via 3C60* were evaluated to be 0.10 eV, while those of the charge-recombination process were estimated to be 0.03 eV in THF and benzonitrile. These low activation energies are one of the characteristics of through-space electron transfer in the rotaxanes.

  我们合成了一种含有[60]富勒烯（C60）和 N,N-双（4-联苯）苯胺（BBA）分子的轮烷。在这种结构中，作为电子受体的 C60 连接到冠醚环上，而两端作为电子供体的末端 BBA 分子穿过冠醚环的轴。这种轮烷的轴中心有一个中性酰胺分子，其中两个 BBA 分子起阻挡作用。在改变溶剂极性和温度的情况下，通过时间分辨瞬态吸收和荧光测量，研究了 C60 和 BBA 分子在轮烷内部光诱导的电子转移过程。轮烷的时间分辨瞬态吸收测量结果证实，在极性溶剂中，长寿命电荷分离态（C60--; BBA-+）轮烷是通过 C60 的激发单线态和三线态（分别为 1C60* 和 3C60*）形成的。经评估，通过 1C60* 和 3C60* 电荷分离过程的速率常数分别为 (3.6-3.7) × 108 s-1 和 (5.1-5.6) × 107 s-1，其比例为 (0.36-0.38): (0.43-0.51)。电荷重组的速率常数分别为 2.5 × 106 s-1 和 4.4 × 106 s-1，对应于电荷分离态在 THF 和苯甲腈中的寿命分别为 400 ns 和 230 ns。根据温度相关性，通过 3C60* 进行电荷分离过程的活化自由能变化被估算为 0.10 eV，而在 THF 和苯甲腈中进行电荷重组过程的活化自由能变化被估算为 0.03 eV。这些低活化能是轮烷中通过空间电子转移的特征之一。
• Influence of extrinsic and intrinsic parameters onto the formation of surface relief gratings in polar azo molecular glasses
  作者：Aurélie Jacquart、Edouard Morin、Feng Yang、Bernard Geffroy、Eléna Ishow

  DOI：10.1016/j.dyepig.2011.04.001

  日期：2012.2