4,4-difluoro-8-(4-bromophenyl)-3,5-diethyl-4-bora-3a,4a-diaza-s-indacene | 1126901-42-5

• 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: 4,4-difluoro-8-(4-bromophenyl)-3,5-diethyl-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 8-(4-bromophenyl)-3,5-diethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene；8-(4-Bromophenyl)-4,12-diethyl-2,2-difluoro-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 1126901-42-5
• 化学式: C₁₉H₁₈BBrF₂N₂
• 分子量: 403.077
• InChiKey: LBBLAVVSUTWDAY-UHFFFAOYSA-N

物化性质

• 熔点：
  135-136 °C(Solvent: Ligroine; Dichloromethane)

计算性质

• 辛醇/水分配系数(LogP)：
  5.24
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  7.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,4-difluoro-8-(4-bromophenyl)-3,5-diethyl-4-bora-3a,4a-diaza-s-indacene 、 4-硼酸三苯胺 在 四(三苯基膦)钯 、 sodium carbonate 作用下， 以 乙二醇二甲醚 、 水 为溶剂， 以81%的产率得到4-[4-(4,12-diethyl-2,2-difluoro-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaen-8-yl)phenyl]-N,N-diphenylaniline
  参考文献：
  名称：

  Novel meso-Polyarylamine-BODIPY Hybrids: Synthesis and Study of Their Optical Properties

  摘要：

  A series of 14 meso-polyarylamine-BODIPY (borondipyrromethene) hybrids of the general structure A were synthesized. Two methods were used to prepare them. The first protocol involved a direct Liebeskind-Srogl cross-coupling of thiomethylbodipys 1-2 with arylaminoboronic acids (4 examples, 75-98%). The second method involves a two-step sequence: a Liebeskind-Srogl reaction to prepare 6 meso-bromoarylbodipys (58-83%) followed by a Suzuki coupling of these Br-containing BODIPYs with arylaminoboronic acids (10 examples, 44-84%). Seven of these derivatives displayed emission in the near-infrared region. The optical properties of compound 18 were rationalized in terms of its crystal structure.

  DOI：

  10.1021/jo802519b
• 作为产物：
  描述：

  、 4-溴苯硼酸 在 tris-(dibenzylideneacetone)dipalladium(0) 、 噻吩-2-甲酸亚铜(I) 、 三(2-呋喃基)膦 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以58%的产率得到4,4-difluoro-8-(4-bromophenyl)-3,5-diethyl-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  Scope and Limitations of the Liebeskind–Srogl Cross-Coupling Reactions Involving the Biellmann BODIPY

  摘要：

  Several new examples of meso-(het)aryIBODIPY were prepared via the Liebeskind-Srogl (L-S) cross-coupling reaction of the Biellmann BODIPYs (1a,b) and aryl- and heteroarylboronic acids in good to excellent yield. It was shown that this reaction could be carried out under microwave heating to shorten reaction times and/or increase the yield. It was illustrated that organostannanes also participate in the L-S reaction to give the corresponding BODIPY analogues in short reaction times and also with good to excellent yields. We analyze the role of the substituent at the sensitive meso position in the photophysical signatures of these compounds. In particular, the rotational motion of the aryl ring and the electron donor ability of the anchored moieties rule the nonradiative pathways and, hence, have a deep impact in the fluorescence efficiency.

  DOI：

  10.1021/acs.joc.5b00731

文献信息

• Synthesis, electrochemical/photophysical properties and computational investigation of 3,5-dialkyl BODIPY fluorophores
  作者：Yavuz Derin、Raşit Fikret Yılmaz、İbrahim Halil Baydilek、Vildan Enisoğlu Atalay、Abdil Özdemir、Ahmet Tutar

  DOI：10.1016/j.ica.2018.06.006

  日期：2018.10

  A series of 3,5 dimethyl and diethyl BODIPY with different substitutions at meso position are synthesized and characterized. Photophysical and electrochemical features of the 3,5 dialkyl BODIPY fluorophores are investigated using experimental and computational approaches. All fluorophores display absorption maxima around at 510 nm and emission maxima around at 520 nm which correspound to very narrow Stokes shift. Among the fluorophores, 3,5,8 alkylated BODIPYs are found to have high fluorescence quantum yield (1.00-0.93). 4-Bromophenyl group at meso position decreases fluorescence quantum yield of the dye while it increases with 4-methoxyphenyl group at meso position. The HOMO-LUMO energies of synthesized fluorophore compounds were calculated by B3LYP/6-31G(d, p) and B3LYP/6-311+ G(d, p) levels in chloroform phase. Electron donating and accepting groups show increasing and decreasing effect on the band gaps of the fluorophores respectively.
• A Solution‐Processable <i>meso</i> ‐Phenyl‐BODIPY‐Based <i>n</i> ‐Channel Semiconductor with Enhanced Fluorescence Emission
  作者：Emrah Ozcan、Mehmet Ozdemir、Dongil Ho、Yunus Zorlu、Resul Ozdemir、Choongik Kim、Hakan Usta、Bunyemin Cosut

  DOI：10.1002/cplu.201900317

  日期：2019.9

  AbstractThe molecular design, synthesis, and characterization of an acceptor‐donor‐acceptor (A‐D‐A) semiconductor BDY‐Ph‐2T‐Ph‐BDY comprising a central phenyl‐bithiophene‐phenyl π‐donor and BODIPY π‐acceptor end‐units is reported. The semiconductor shows an optical band gap of 2.32 eV with a highly stabilized HOMO/LUMO (−5.74 eV/−3.42 eV). Single‐crystal X‐ray diffraction (XRD) reveals D–A dihedral angle of ca. 66° and strong intermolecular “C−H ⋅⋅⋅ π (3.31 Å)” interactions. Reduced π‐donor strength, increased D–A dihedral angle, and restricted intramolecular D–A rotations allows for both good fluorescence efficiency (ΦF=0.30) and n‐channel OFET transport (μe=0.005 cm2/V ⋅ s; Ion/Ioff=104–105). This indicates a much improved (6‐fold) fluorescence quantum yield compared to the meso‐thienyl BODIPY semiconductor BDY‐4T‐BDY. Photophysical studies reveal important transitions between locally excited (LE) and twisted intramolecular charge‐transfer (TICT) states in solution and the solid state, which could be controlled by solvent polarity and nano‐aggregation. This is the first report of such high emissive characteristics for a BODIPY‐based n‐channel semiconductor.
• Novel <i>meso</i>-Polyarylamine-BODIPY Hybrids: Synthesis and Study of Their Optical Properties
  作者：Erik Lager、Jianzhao Liu、Angélica Aguilar-Aguilar、Ben Zhong Tang、Eduardo Peña-Cabrera

  DOI：10.1021/jo802519b

  日期：2009.3.6

  A series of 14 meso-polyarylamine-BODIPY (borondipyrromethene) hybrids of the general structure A were synthesized. Two methods were used to prepare them. The first protocol involved a direct Liebeskind-Srogl cross-coupling of thiomethylbodipys 1-2 with arylaminoboronic acids (4 examples, 75-98%). The second method involves a two-step sequence: a Liebeskind-Srogl reaction to prepare 6 meso-bromoarylbodipys (58-83%) followed by a Suzuki coupling of these Br-containing BODIPYs with arylaminoboronic acids (10 examples, 44-84%). Seven of these derivatives displayed emission in the near-infrared region. The optical properties of compound 18 were rationalized in terms of its crystal structure.
• Scope and Limitations of the Liebeskind–Srogl Cross-Coupling Reactions Involving the Biellmann BODIPY
  作者：Lourdes Betancourt-Mendiola、Ismael Valois-Escamilla、Teresa Arbeloa、Jorge Bañuelos、Iñigo López Arbeloa、Juan O. Flores-Rizo、Rongrong Hu、Erik Lager、César F. A. Gómez-Durán、José L. Belmonte-Vázquez、Mayra R. Martínez-González、Ismael J. Arroyo、Carlos A. Osorio-Martínez、Enrique Alvarado-Martínez、Arlette Urías-Benavides、Brenda D. Gutiérrez-Ramos、Ben Zhong Tang、Eduardo Peña-Cabrera

  DOI：10.1021/acs.joc.5b00731

  日期：2015.6.5

  Several new examples of meso-(het)aryIBODIPY were prepared via the Liebeskind-Srogl (L-S) cross-coupling reaction of the Biellmann BODIPYs (1a,b) and aryl- and heteroarylboronic acids in good to excellent yield. It was shown that this reaction could be carried out under microwave heating to shorten reaction times and/or increase the yield. It was illustrated that organostannanes also participate in the L-S reaction to give the corresponding BODIPY analogues in short reaction times and also with good to excellent yields. We analyze the role of the substituent at the sensitive meso position in the photophysical signatures of these compounds. In particular, the rotational motion of the aryl ring and the electron donor ability of the anchored moieties rule the nonradiative pathways and, hence, have a deep impact in the fluorescence efficiency.