1,3,5-tribromo-2,4,6-tris[p-(N,N-di-n-octylamino)phenylethynyl]benzene | 684216-74-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,3,5-tribromo-2,4,6-tris[p-(N,N-di-n-octylamino)phenylethynyl]benzene
• 英文别名: 1,3,5-tribromo-2,4,6-tris(p-dioctylaminophenylethynyl)benzene
• CAS: 684216-74-8
• 化学式: C₇₈H₁₁₄Br₃N₃
• 分子量: 1333.5
• InChiKey: YNNRNAKYFFNWMD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  24.76
• 重原子数：
  84.0
• 可旋转键数：
  45.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  9.72
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2-(4-ethynylphenyl)-1,3-dioxolane 、 1,3,5-tribromo-2,4,6-tris[p-(N,N-di-n-octylamino)phenylethynyl]benzene 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 三乙胺 、 三苯基膦 作用下， 反应 87.0h， 以23%的产率得到1,3,5-tris[p-(N,N-di-n-octylamino)phenylethynyl]-2,4,6-tris[p-(1,3-dioxolan-2-yl)phenylethynyl]benzene
  参考文献：
  名称：

  Synthesis and Self-Association, Absorption, and Fluorescence Properties of Differentially Functionalized Hexakis(p-substituted-phenylethynyl)benzenes

  摘要：

  The dual Sonogashira coupling reactions of 1,3,5-tribromo-2,4,6-triiodobenzene with p-X-phenylacetylene followed by another p-Y-phenylacetylene (X, Y = OsiMe(2)Bu-t or CO2Et) produced a series of differentially functionalized hexakis(p-substituted-phenylethynyl)benzenes with D-3h symmetry (3h: 1,3,5-X-2,4,6-Y) and C-2nu symmetry (3g,i: 1,2,3,5-X-4,6-Y; 3f,j: 1-X-2,3,4,5,6-Y). In a similar manner, 1,3,5-tris(p-X-phenylethynyl)-2,4,6-tris(p-Y-phenylethynyl)benzenes and 1,2,3,5-tetrakis(p-X-phenylethynyl)-4,6-bis(p-Y-phenylethynyl)benzenes (31: X = OSiMe2Bu-t, Y = NO2; 3m,n: X = N(n-octyl)(2), Y = NO2; 3o,p: X = N(n-octyl)(2), Y = CH(OCH2CH2O); 3q,r: X = N(n-octyl)(2), Y = CHO; 3s,t: X = N(n-octyl)(2), Y = CH=C(CN)(2)) were prepared. Compounds 3 with electron-withdrawing groups self-aggregated by a pi-pi stacking interaction and solvophobic effect. In the absorption and fluorescence spectra of 3, lambda(max)(abs) and lambda(max)(em) showed red shifts as the donor-acceptor dipole at the end functional groups of the para position was increased. In the absorption spectra, lambda(max)(abs) showed red shifts upon increasing the number of combination of electron-donating and -withdrawing groups on the diagonal line in a molecule, whereas lambda(max)(em) in the fluorescence spectra exhibited red shifts upon decreasing the molecular symmetry.

  DOI：

  10.1021/jo049948s
• 作为产物：
  描述：

  1,3,5-三溴-2,4,6-三碘苯 、 4-ethynyl-N,N-dioctylaniline 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 三乙胺 、 三苯基膦 作用下， 反应 43.0h， 以57%的产率得到1,3,5-tribromo-2,4,6-tris[p-(N,N-di-n-octylamino)phenylethynyl]benzene
  参考文献：
  名称：

  Synthesis and Self-Association, Absorption, and Fluorescence Properties of Differentially Functionalized Hexakis(p-substituted-phenylethynyl)benzenes

  摘要：

  The dual Sonogashira coupling reactions of 1,3,5-tribromo-2,4,6-triiodobenzene with p-X-phenylacetylene followed by another p-Y-phenylacetylene (X, Y = OsiMe(2)Bu-t or CO2Et) produced a series of differentially functionalized hexakis(p-substituted-phenylethynyl)benzenes with D-3h symmetry (3h: 1,3,5-X-2,4,6-Y) and C-2nu symmetry (3g,i: 1,2,3,5-X-4,6-Y; 3f,j: 1-X-2,3,4,5,6-Y). In a similar manner, 1,3,5-tris(p-X-phenylethynyl)-2,4,6-tris(p-Y-phenylethynyl)benzenes and 1,2,3,5-tetrakis(p-X-phenylethynyl)-4,6-bis(p-Y-phenylethynyl)benzenes (31: X = OSiMe2Bu-t, Y = NO2; 3m,n: X = N(n-octyl)(2), Y = NO2; 3o,p: X = N(n-octyl)(2), Y = CH(OCH2CH2O); 3q,r: X = N(n-octyl)(2), Y = CHO; 3s,t: X = N(n-octyl)(2), Y = CH=C(CN)(2)) were prepared. Compounds 3 with electron-withdrawing groups self-aggregated by a pi-pi stacking interaction and solvophobic effect. In the absorption and fluorescence spectra of 3, lambda(max)(abs) and lambda(max)(em) showed red shifts as the donor-acceptor dipole at the end functional groups of the para position was increased. In the absorption spectra, lambda(max)(abs) showed red shifts upon increasing the number of combination of electron-donating and -withdrawing groups on the diagonal line in a molecule, whereas lambda(max)(em) in the fluorescence spectra exhibited red shifts upon decreasing the molecular symmetry.

  DOI：

  10.1021/jo049948s

文献信息

• Synthesis and Optical Properties, Including Two-Photon Absorption Cross-Sections, of Differentially Functionalized Starburst-Type π-Conjugated Molecules
  作者：Kenji Kobayashi、Yuto Kita、Motoyuki Shigeiwa、Satoru Imamura、Shuuichi Maeda

  DOI：10.1246/bcsj.82.1416

  日期：2009.11.15

  Differentially functionalized hexakis( p-substituted-phenylethynyl)benzene and hexakis[4-( p-substituted-styryl)phenylethynyl]benzene derivatives with various (D6h, D3h, D2h, and C2v) symmetries were synthesized by Sonogashira cross-coupling reactions. The optical properties of this starburst-type π-conjugated system were investigated. Among them, hexakis[4-( p-dioctylaminostyryl)phenylethynyl]benzene (5) showed the largest two-photon absorption cross-section of δ = 818 GM at 800 nm, which was determined by open aperture Z-scan with 120 fs laser pulses in toluene solution.

  通过 Sonogashira 交叉偶联反应合成了不同对称性（D6h、D3h、D2h 和 C2v）的不同官能化六(对取代苯乙炔基)苯和六[4-(对取代苯乙烯基)苯乙炔基]苯衍生物。研究了这种星爆型 π 共轭体系的光学性质。其中，六[4-( 对二辛基氨基苯乙烯基)苯乙炔基]苯（5）在 800 纳米波长处显示出最大的双光子吸收截面δ = 818 GM，这是通过在甲苯溶液中使用 120 fs 激光脉冲进行开孔 Z 扫描测定的。