1,3,5,7-tetra(Bpin)azulene | 1187945-48-7

• 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: 1,3,5,7-tetra(Bpin)azulene
• 英文别名: 4,4,5,5-Tetramethyl-2-[1,3,7-tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)azulen-5-yl]-1,3,2-dioxaborolane
• CAS: 1187945-48-7
• 化学式: C₃₄H₅₂B₄O₈
• 分子量: 632.026
• InChiKey: MDUSHQZCHFYWJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  46
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  73.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,3,5,7-tetra(Bpin)azulene 在 三氟乙酸 作用下， 以 乙酸乙酯 为溶剂， 生成 5,7-di(Bpin)azulene
  参考文献：
  名称：

  机械化学生成的 C60-富勒烯与四-(5,7-二苯基)杯[4]芘的固态络合物、NMR、XRD 和 DFT 研究

  摘要：

  摘要 描述了通过5,7-二苯基芴与甲醛反应合成四(5,7-二苯基)杯[4]芴。通过固态 13C-NMR 光谱和 X 射线粉末衍射评估了通过研磨两种组分产生的与 C60 的固态超分子络合。报告了可能结构的气相 DFT 研究。

  DOI：

  10.1080/10610278.2017.1415435
• 作为产物：
  描述：

  1,3,5-tris(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)azulene 、 联硼酸频那醇酯 在 2,2'-联吡啶 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 作用下， 以 环己烷 为溶剂， 以4%的产率得到1,3,5,7-tetra(Bpin)azulene
  参考文献：
  名称：

  Polyborylation of azulenes

  摘要：

  In the presence of an active Ir-based catalyst, azulene underwent stepwise borylation with bis(pinacolato)diboron to produce polyborylated products. The reactivity of the ring atoms toward borylation was found to decrease in the following order: 2-position>1,3-positiotls>6-position>5,7-positions. Extension of the borylation to some azulenes Substituted at the five-membered ring was also examined. Furthermore, the reaction of 2,6-bis(4,4,5.5-tetramethyl-1,3,2-dioxaborolanyl)azulene (3a) with an equivalent of hydrogen peroxide revealed that the oxidation proceeds preferentially at the 6-position. This indicates that the reactivity of the boryl group is governed by the pi-polarization of the azulenyl skeleton. (C) 2009 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2009.06.053

文献信息

• Influence of Alkoxy Chain Length on the Properties of Two‐Dimensionally Expanded Azulene‐Core‐Based Hole‐Transporting Materials for Efficient Perovskite Solar Cells
  作者：Minh Anh Truong、Jaehyun Lee、Tomoya Nakamura、Ji‐Youn Seo、Mina Jung、Masashi Ozaki、Ai Shimazaki、Nobutaka Shioya、Takeshi Hasegawa、Yasujiro Murata、Shaik Mohammed Zakeeruddin、Michael Grätzel、Richard Murdey、Atsushi Wakamiya

  DOI：10.1002/chem.201806317

  日期：2019.5.10

  of two‐dimensionally expanded azulene‐core‐based π systems have been synthesized with different alkyl chain lengths in the alkoxy moieties connected to the partially oxygen‐bridged triarylamine skeletons. The thermal, photophysical, and electronic properties of each compound were evaluated to determine the influence of the alkyl chain length on their effectiveness as hole‐transporting materials (HTMs)

  已经合成了一系列二维扩展的基于z烯核的π系统，这些烷基系统在与部分氧桥连的三芳基胺骨架连接的烷氧基部分具有不同的烷基链长。评估了每种化合物的热，光物理和电子性质，以确定烷基链长度对其在钙钛矿太阳能电池（PSC）中作为空穴传输材料（HTM）的有效性的影响。所有合成的分子均显示出令人鼓舞的材料特性，包括高溶解度，平坦和无定形膜的形成以及能级与钙钛矿的最佳对准。特别是甲基和n的衍生物侧链中的丁基丁基分别保持高达233和159°C的非晶态稳定性。这样的短烷氧基链也导致改善的电子器件性能。用具有正丁基侧链的HTM制成的PSC装置表现出最佳性能，功率转换效率为18.9％，与基于spiro-OMeTAD的PSC（spiro-OMeTAD = 2,2'，7， 7'-四[[ N，N-双（对-甲氧基苯基）氨基] -9,9'-螺二芴）。
• Isomeric Dual-Pore Two-Dimensional Covalent Organic Frameworks
  作者：Boxu Feng、Xiyu Chen、Pu Yan、Senhe Huang、Chenbao Lu、Huiping Ji、Jinhui Zhu、Zhi Yang、Kecheng Cao、Xiaodong Zhuang

  DOI：10.1021/jacs.3c09559

  日期：2023.12.13

  Two-dimensional (2D) covalent organic frameworks (COFs) with hierarchical porosity have been increasingly recognized as promising materials in various fields. Besides, the 2D COFs with kagome (kgm) topology can exhibit unique optoelectronic features and have extensive applications. However, rational synthesis of the COFs with kgm topology remains challenging because of competition with a square-lattice

  具有分级孔隙率的二维（2D）共价有机框架（COF）已被越来越多地认为是各个领域有前途的材料。此外，具有kagome（ kgm ）拓扑的2D COF可以表现出独特的光电特性并具有广泛的应用。然而，由于与方晶格拓扑的竞争，合理合成具有kgm拓扑的 COF 仍然具有挑战性。在此，我们报告了两种具有kgm拓扑的异构双孔 2D COF，使用一种新颖的几何策略来降低其构建块的对称性，这些构建块是基于四臂萘和基于甘菊环的异构单体。由于薁的大偶极矩，所制备的薁基COF（COF-Az）具有相当窄的带隙，低至1.37 eV，比萘基2D COF（COF-Nap：2.28）窄得多。 eV），是已报道的亚胺连接双孔二维 COF 中带隙最低的。此外，COF-Az用作气体传感器中的电极材料，对NO 2表现出高选择性，包​​括对NO 2 (10 ppm)的高响应率(58.7%)、快速恢复(72秒)、长达10周稳定性和耐 80%
• Hole-Transporting Materials with a Two-Dimensionally Expanded π-System around an Azulene Core for Efficient Perovskite Solar Cells
  作者：Hidetaka Nishimura、Naoki Ishida、Ai Shimazaki、Atsushi Wakamiya、Akinori Saeki、Lawrence T. Scott、Yasujiro Murata

  DOI：10.1021/jacs.5b11008

  日期：2015.12.23

  Two-dimensionally expanded pi-systems, consisting of partially oxygen-bridged triarylamine skeletons that are connected to an azulene (1-3) or biphenyl core (4), were synthesized and characterized. When tetra-substituted azulene 1 was used as a hole-transporting material (HTM) in perovskite solar cells, the observed performance (power conversion efficiency = 16.5%) was found to be superior to that of the current HTM standard Spiro-OMeTAD. A comparison of the hole mobility, the ability to control the HOMO and LUMO levels, and the hole-collection efficiency at the perovskite/HTM interface in 1 with reference compounds (2-4 and Spiro-OMeTAD) led to the elucidation of key factors required for HTMs to act efficiently in perovskite solar cells.
• 1,3,5,7-Tetra(Bpin)azulene by Exhaustive Direct Borylation of Azulene and 5,7-Di(Bpin)azulene by Selective Subsequent Deborylation
  作者：Lawrence Scott、Hidetaka Nishimura、Maria Eliseeva、Atsushi Wakamiya

  DOI：10.1055/s-0034-1380686

  日期：——

  Exhaustive borylation of azulene with excess bis(pinacolato)-diboron (B(2)pin(2)) under conditions that promote equilibration of the borylated azulenes provides a convenient one-step synthesis of 1,3,5,7-tetra(Bpin)azulene as the major product. The Bpin substituents at positions 1 and 3 can be conveniently removed from 1,3,5,7-tetra-(Bpin)azulene by treatment with trifluoroacetic acid at room temperature to give 5,7-di(Bpin)azulene. The utility of 5,7-di(Bpin)azulene as a synthetic precursor to 5,7-disubstituted azulenes that are otherwise difficult to access is demonstrated by Suzuki coupling to give the previously unknown 5,7-diphenylazulene.