4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a-diaza-s-indacene | 154793-50-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 3,3',5,5'-tetraphenyl-2,2'-dipyrrolylmethene difluoroborate；1,3,5,7-tetraphenyldipyrrolylmethenmethene difluoroborate；difluoroborate 3,3',5,5'-tetraphenyl-2,2'-dipyrrolylmetene；1,3,5,7-tetraphenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene；2,2-Difluoro-4,6,10,12-tetraphenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene；2,2-difluoro-4,6,10,12-tetraphenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 154793-50-7
• 化学式: C₃₃H₂₃BF₂N₂
• 分子量: 496.367
• InChiKey: KZXRLXQQFZUZTL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.0
• 重原子数：
  38
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  7.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2,4-二苯基吡咯 在 乙酸酐 、 三乙胺 、 三氯氧磷 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 5.5h， 生成 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  Synthesis, spectral-luminescent properties of B(III) and Zn(II) complexes with alkyl- and aryl-substituted dipyrrins and azadipyrrins

  摘要：

  Effect of complexing atom, molecular structure of dipyrrolylmethene and its aza analog on spectral-luminescent properties of heteroleptic boron(III) and homoleptic zinc(II) complexes with 3,3',5,5'-tetramethyl-2,2'-dipyrrolylmethene, 3,3',5,5'-tetraphenyl-2,2'-dipyrrolylmethene, and 3,3',5,5'-tetraphenyl-ms-aza-2,2'-dipyrrolylmethene in organic solvent solutions was studied. The complexes were found to exhibit strong chromophore (lambda = 350-690 nm, E > similar to 10(5) L/mol cm) and fluorescent properties. Quantum yield (gamma(fl)) for fluoroborate complexes reaches 100% and is weakly dependent on medium nature. The value of gamma(fl) for phenyl- and alkyl-substituted zinc(II) dipyrrolylmethenates in nonpolar solvents is not higher 0.3 and 0.03, respectively; complete fluorescence quenching is observed in electron-donating solvents. Aza-substitution at the meso spacer causes considerable shift of electronic absorption and fluorescence spectra to the red region but completely quenches fluorescence of zinc(II) chelates and decreases gamma(fl) of boron(III) complex to 0.04.

  DOI：

  10.1134/s0036023614100027

文献信息

• A new synthesis of symmetric boraindacene (BODIPY) dyes
  作者：Liangxing Wu、Kevin Burgess

  DOI：10.1039/b810503k

  日期：——

  BODIPY dyes were synthesized from pyrrole-2-carbaldehyde derivatives in high yields; this constitutes a new approach to this dye framework.

  BODIPY染料是从吡咯-2-醛衍生物高产率合成的；这构成了一种新的染料框架合成方法。
• Effect of Aryl-, Halogen-, and Ms-Aza-Substitution on the Luminescent Properties and Photostability of Difluoroborates of 2,2′-Dipyrrometenes
  作者：Anna Yu. Kritskaya、Mikhail B. Berezin、Elena V. Antina、Anatoly I. Vyugin

  DOI：10.1007/s10895-019-02403-2

  日期：2019.7

  to 5–20%. The stability of 2,2′-dipyrromethenes difluoroborates to oxidative destruction under the influence of UV irradiation in cyclohexane solutions was evaluated. It has been shown that symmetric aryl substitution in pyrrole cycles of dipyrromethene significantly increases the photostability of the corresponding compounds as compared to alkyl-substituted analogs and is an effective method of obtaining

  合成了具有烷基，苯基和卤素取代的2,2'-二吡咯烷酮（BODIPY）和内消旋氮杂双吡咯烷酮（ms-aza-BODIPY）的硼（III）配合物。分析了所获得的配位化合物与其发光特性的结构关系。与烷基取代的类似物相比，丙烯酸化的BODIPY对与溶剂的粒子间相互作用更敏感，从而导致量子产率最多降低40％。在BODIPY分子中引入苯基​​取代基会使第一个吸收带发生红移，显着（32-37 nm）增加了发射光谱的斯托克斯位移，但降低了S 0  →S 1的可能性与烷基化配合物相比，电子跃迁。与BODIPY相比，用氮取代次甲基碳原子会导致ms-aza-BODIPY荧光猝灭，最高可达5-20％。评价了2,2'-吡咯并蒽二氟硼酸盐在环己烷溶液中的紫外线照射下对氧化破坏的稳定性。已经显示，与烷基取代的类似物相比，在二吡咯亚甲基的吡咯循环中的对称芳基取代显着增加了相应化合物的光稳定性，并且是获得具有实际有用性能的
• Aza-BODIPY: Improved synthesis and interaction with soluble Aβ1–42 oligomers
  作者：Laramie P. Jameson、Sergei V. Dzyuba

  DOI：10.1016/j.bmcl.2013.01.065

  日期：2013.3

  Dye-binding assays that are used to evaluate anti-aggregation ability of small molecule inhibitors towards amyloids are known to be prone to false-positive effects due to spectral overlaps between the dye and the inhibitor. Aza-BODIPY dye, which has both excitation and emission maxima above 600 nm, exhibits a significant increase in its fluorescence intensity in the presence of soluble oligomers of A beta 1-42. These results indicate that aza-BODIPY could serve as a near-IR probe for detecting conformational changes of A beta 1-42 soluble oligomers in vitro, and it should eliminate false-positive effects that are associated with currently utilized thioflavin T-based dyes. In addition, a facile synthesis of aza-BODIPY has been developed, which might further expand the applications of this dye. (C) 2013 Elsevier Ltd. All rights reserved.
• Effect of Alkyl, Aryl, and meso-Aza Substitution on the Thermal Stability of BODIPY
  作者：N. A. Bumagina、A. Yu. Kritskaya、E. V. Antina、M. B. Berezin、A. I. V’yugin

  DOI：10.1134/s0036023618100030

  日期：2018.10

  The effect of peripheral alkyl, aryl, and meso-aza substitution on the thermal stability of BODIPYs in an argon or oxygen atmosphere has been analyzed using thermogravimetric study results. It has been shown that an increase in the length of 2,6-alkyl substituents to seven carbon atoms is accompanied by the growth of BODIPY thermal stability by 80 degrees C. The greatest increase in the destruction temperature of BODIPY (by 100 degrees C) is attained via the introduction of phenyl groups in the 1,3,5,7-positions of its dipyrromethenmethene framework. meso-Aza substitution does not almost produce any effect on the thermal stability of BODIPY dyes. The BODIPY destruction beginning temperature decreases by 60-90 degrees C in the presence of air oxygen. The thermal stability of BODIPY tends to decrease with reducing degree and symmetry of alkyl substitution in the dipyrromethene framework. A lower thermal stability of BODIPY in comparison with zinc(II) dipyrromethenates is due to the participation of fluorine atoms in intramolecular redox processes.
• The computational and experimental investigations of photophysical and spectroscopic properties of BF2 dipyrromethene complexes
  作者：R.R. Valiev、A.N. Sinelnikov、Y.V. Aksenova、R.T. Kuznetsova、M.B. Berezin、A.S. Semeikin、V.N. Cherepanov

  DOI：10.1016/j.saa.2013.08.042

  日期：2014.1

  The electronic excited states of BF2 dipyrromethene (2BrDPM, DPMI, DPMII, PM567 and 4PhDPM) complexes were investigated using the extended multi-configuration quasi-degenerate at the second order of perturbation theory (XMCQDPT2) and the second-order approximate coupled-cluster (CC2) methods. The excitation energies calculated by CC2 are significantly overestimated by 0.42-0.59 eV because of the substantial contributions of double excitation levels to excited states (>10%). However, the calculated XMCQDPT2 excitation energies agree well with experimental ones within the accuracy 0.11-0.20 eV. The very low lasing efficiency (7.8-8.4%) of 4PhDPM compound was explained by the T-1 -> T-4 and T-1 -> T-5 reabsorptions at XMCQDPT2 level of theory. The molecular photonics of pyrromethenes are studied using a combination of the first-principle and semi-empirical calculations. The main mechanism for the deactivation of the energy of the first singlet excited electronic state is the radiative electronic transition for DPMI, DPMII, PM567 and 4PhDPM compounds. Also, the main mechanism for the quenching of fluorescence in considered complexes (except DPMII compound) is the internal conversion. The processes of the internal conversion and intersystem crossing compete with each other in DPMII compound. The measured and calculated fluorescence quantum yields agree well for all considered molecules. (C) 2013 Elsevier B.V. All rights reserved.