N,N-difluoroboryl-[N-(3-phenyl-2H-isoindol-1-yl)-N-(3-phenyl-1H-isoindol-1-ylidene)amine] | 1073151-42-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: N,N-difluoroboryl-[N-(3-phenyl-2H-isoindol-1-yl)-N-(3-phenyl-1H-isoindol-1-ylidene)amine]
• 英文别名: 12,12-Difluoro-10,14-diphenyl-2,13-diaza-11-azonia-12-boranuidapentacyclo[11.7.0.03,11.04,9.015,20]icosa-1(20),2,4,6,8,10,14,16,18-nonaene；12,12-difluoro-10,14-diphenyl-2,13-diaza-11-azonia-12-boranuidapentacyclo[11.7.0.03,11.04,9.015,20]icosa-1(20),2,4,6,8,10,14,16,18-nonaene
• CAS: 1073151-42-4
• 化学式: C₂₈H₁₈BF₂N₃
• 分子量: 445.279
• InChiKey: AASCZYFUWWLVSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.49
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N,N-difluoroboryl-[N-(3-phenyl-2H-isoindol-1-yl)-N-(3-phenyl-1H-isoindol-1-ylidene)amine] 、 三氯化硼 以 二氯甲烷 为溶剂， 反应 0.33h， 以100%的产率得到N,N-dichloroboryl-[N-(3-phenyl-2H-isoindol-1-yl)-N-(3-phenyl1H-isoindol-1-ylidene)amine]
  参考文献：
  名称：

  Synthesis, properties and reactivity of BCl₂ aza-BODIPY complexes and salts of the aza-dipyrrinato scaffold

  摘要：

  将F-aza-BODIPYs转化为Cl-aza-BODIPYs可使硼处于易位状态，使用芳基格氏试剂进行取代，同时进行受控的脱硼去保护作用，从而得到母体azadipyrrin。

  DOI：

  10.1039/d0ob00272k
• 作为产物：
  描述：

  溴苯 在 碘 、 magnesium 、 N,N-二异丙基乙胺 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 6.5h， 生成 N,N-difluoroboryl-[N-(3-phenyl-2H-isoindol-1-yl)-N-(3-phenyl-1H-isoindol-1-ylidene)amine]
  参考文献：
  名称：

  Synthesis and Charge-Transfer Dynamics in a Ferrocene-Containing Organoboryl aza-BODIPY Donor–Acceptor Triad with Boron as the Hub

  摘要：

  A N,N'-bis(ferroceneacetylene)boryl complex of 3,3'-diphenylazadiisoindolylmethene was synthesized by the reaction of an N,N'-difluoroboryl complex of 3,3'-diphenylazadiisoindolylmethene and ferroceneacetylene magnesium bromide. The novel diiron complex was characterized by a variety of spectroscopic techniques, electrochemistry, and ultrafast time-resolved methods. Spectroscopy and redox behavior was correlated with the density functional theory (DFT) and time-dependent DFT calculations. An unexpected degree of coupling between the two Fc ligands was observed. Despite a lack of conjugation between the donor and acceptor, the complex undergoes very rapid (tau = 1.7 +/- 0.1 ps) photoinduced intramolecular charge separation followed by subpicosecond charge recombination to form a triplet state with a lifetime of 4.8 +/- 0.1 mu s.

  DOI：

  10.1021/acs.inorgchem.5b00494

文献信息

• Synthesis and Characterization of Near-Infrared Absorbing Benzannulated Aza-BODIPY Dyes
  作者：Roland Gresser、Markus Hummert、Horst Hartmann、Karl Leo、Moritz Riede

  DOI：10.1002/chem.201002941

  日期：2011.3.1

  synthesized by the addition of aryl Grignard compounds to phthalodinitrile and subsequent reaction with formamide. A plausible reaction mechanism, through a Leuckart–Wallach‐type reduction has been confirmed by means of DFT calculations of the related transition and intermediate states. The corresponding boron difluoride complexes (10) of 9 were prepared in a subsequent reaction step and the spectroscopic and

  通过在苯二腈中添加芳基格氏化合物并随后与甲酰胺反应，合成了一系列新颖的氮杂二异吲哚甲胺染料9，它们在吲哚部分具有六个不同的芳基和杂芳基。通过相关过渡态和中间态的DFT计算，已经证实了通过Leuckart-Wallach型还原的合理反应机理。在随后的反应步骤中制备了相应的9的二氟化硼配合物（10），并通过实验和理论研究了9和10的光谱和电化学性质。氮杂二异吲哚胺9它们的最大吸收在615至720nm范围内，而配合物10在681至793nm之间呈现出红移的最大吸收峰。通过循环伏安法测得的9和10显示出完全可逆的氧化还原波，用于还原和氧化，且电势较高，为10。根据测得的氧化还原电势，计算出9和10的HOMO和LUMO能级。使用DFT计算边界轨道能量，吸收带的能量以及吸收过程中涉及的轨道，并将其与9和10的测量结果进行比较。最大吸收可能与强烈的HOMO-LUMO跃迁有关，复合时LUMO更明显的稳定化
• Chiral benzo-fused Aza-BODIPYs with optical activity extending into the NIR range
  作者：Lu Zhang、Luyang Zhao、Kang Wang、Jianzhuang Jiang

  DOI：10.1016/j.dyepig.2016.07.039

  日期：2016.11

  Fusion of benzene moieties onto the BODIPY periphery in combination with the introduction of peripheral chiral binaphthyl substituents renders the extension of optical activity of resulting chiral benzo-fused aza-BODIPYs into the near-IR (NIR) range, representing the first chiral BODIPYs with NIR optically activity. For comparative study, N,N-difluoroboryl-[N-(3-phenyl-2H-isoindol-1-yl)-N-(3-phenyl-1

  手性苯并稠合的氮杂-BODIPY，即N，N-二氟硼基-[（二萘并[1,2- e：1'，2' - g ] -1,4-二氧辛] -1 [ N-（3-苯基-2H-异吲哚-1-基）亚甲基] -3-苯基-1H-异吲哚-1-亚基）胺]（1）和N，N-二氟硼基-[（二萘并[1,2- e：1'，2 ′ -g ] -1,4-dioxocine）-1-[（二萘并[1,2- e：1'，2' - g ] -1,4-dioxocine）-N-（3-苯基-2H-异吲哚-1-基）亚甲基] -3-苯基-1H-异吲哚-1-亚胺基]]（2），已合成并经光谱表征。苯部分在BODIPY外围的融合以及周围手性双萘基取代基的引入使所得手性苯并稠合的氮杂-BODIPYs的光学活性扩展到近红外（NIR）范围，代表了第一个具有NIR的手性BODIPY光学活性。为了进行比较研究，还制备了N，N-二氟硼基- [ N-（3-苯基-2H-异吲哚-
• Aza-BODIPY Derivatives Containing BF(CN) and B(CN)₂ Moieties
  作者：Tian-yi Li、Zaifei Ma、Zhi Qiao、Christian Körner、Koen Vandewal、Olaf Zeika、Karl Leo

  DOI：10.1002/cplu.201600479

  日期：2017.2

  Two novel aza-BODIPY derivatives are synthesized, with the fluorine atoms in the BF2 moiety replaced by cyano groups. The introduction of cyano groups changes the phenyl substituents on the 3,5 positions from parallel to antiparallel. The HOMO/LUMO energy levels are stabilized gradually upon increasing the number of cyano groups, and the photophysical properties show corresponding shifts. With high

  合成了两种新颖的aza-BODIPY衍生物，其中BF2部分中的氟原子被氰基取代。氰基的引入将3，5位上的苯基取代基从平行变为反平行。随着氰基数量的增加，HOMO / LUMO的能级逐渐稳定，光物理性质显示出相应的变化。具有高的热稳定性，可以通过升华纯化衍生物，并用于制备真空沉积的薄膜。这项研究扩展了具有氰基取代衍生物的aza-BODIPY系列。
• Ultrafast Photoinduced Electron Transfer and Charge Stabilization in Donor–Acceptor Dyads Capable of Harvesting Near‐Infrared Light
  作者：Venugopal Bandi、Habtom B. Gobeze、Francis D'Souza

  DOI：10.1002/chem.201500728

  日期：2015.8.3

  To harvest energy from the near‐infrared (near‐IR) and infrared (IR) regions of the electromagnetic spectrum, which constitutes nearly 70 % of the solar radiation, there is a great demand for near‐IR and IR light‐absorbing sensitizers that are capable of undergoing ultrafast photoinduced electron transfer when connected to a suitable electron acceptor. Towards achieving this goal, in the present study

  为了从构成近70％太阳辐射的电磁光谱的近红外（near-IR）和红外（IR）区域中获取能量，对近红外和红外光吸收敏化剂的需求量很大，当连接到合适的电子受体时，它们能够进行超快的光诱导电子转移。为了实现这一目标，在本研究中，我们报告了由结构修饰的BF 2衍生的二步法的多步合成螯合的氮杂二吡咯甲烷（ADP；将吸收和发射扩展到近红外区域）和富勒烯分别作为电子给体和电子受体实体。基于光吸收，荧光，几何优化和电化学研究，对新合成的二元化合物进行了全面表征。既定的能级图揭示了电子可能从单线态激发的近红外敏化剂或单线态激发的富勒烯转移。飞秒和纳秒瞬态吸收研究旨在收集激发态电子转移的证据，并评估电荷分离和电荷复合过程的动力学。这些研究表明，发生了超快的光诱导电子转移，从而导致了二元组中电荷的稳定，如果是BF 2螯合的二吡咯亚甲基衍生的二元组，则在电荷重组期间为60。目前的发现表明，这些敏化剂适用于从太阳光
• Synthesis and Spectroscopic Properties of Fused-Ring-Expanded Aza-Boradiazaindacenes
  作者：Hua Lu、Soji Shimizu、John Mack、Zhen Shen、Nagao Kobayashi

  DOI：10.1002/asia.201000641

  日期：2011.4.4

  AbstractA series of fused‐ring‐expanded aza‐boradiazaindacene (aza‐BODIPY) dyes have been synthesized by reacting arylmagnesium bromides with phthalonitriles or naphthalenedicarbonitriles. An analysis of the structure–property relationships has been carried out based on X‐ray crystallography, optical spectroscopy, and theoretical calculations. Benzo and 1,2‐naphtho‐fused 3,5‐diaryl aza‐BODIPY dyes display markedly red shifted absorption and emission bands in the near‐IR region (>700 nm) due to changes in the energies of the frontier MOs relative to those of 1,3,5,7‐tetraaryl aza‐BODIPYs. Only one 1,2‐naphtho‐fused aza‐BODIPY of the three possible isomers is formed due to steric effects, and 2,3‐naphtho‐fused compounds could not be characterized because the final BF2 complexes are unstable in solution. The incorporation of a N(CH3)2 group at the para‐positions of a benzo‐fused 3,5‐diaryl aza‐BODIPY quenches the fluorescence in polar solvents and results in a ratiometric pH response, which could be used in future practical applications as an NIR “turn‐on” fluorescence sensor.