E,E-2,5-bis{4-[di(p-anisyl)amino]styryl}-3,4-di(n-butoxy)thiophene | 879206-83-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: E,E-2,5-bis{4-[di(p-anisyl)amino]styryl}-3,4-di(n-butoxy)thiophene
• 英文别名: E,E-2,5-bis[4-{di-(4-methoxyphenyl)amino}styryl]-3,4-di-n-butoxythiophene；E,E-2,5-Bis(4-[bis(4-methoxyphenyl)amino]styryl)-3,4-di(n-butoxy)thiophene；4-[(E)-2-[3,4-dibutoxy-5-[(E)-2-[4-(4-methoxy-N-(4-methoxyphenyl)anilino)phenyl]ethenyl]thiophen-2-yl]ethenyl]-N,N-bis(4-methoxyphenyl)aniline
• CAS: 879206-83-4
• 化学式: C₅₆H₅₈N₂O₆S
• 分子量: 887.152
• InChiKey: KALUUEYJQLFLSE-SMXMXQJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15
• 重原子数：
  65
• 可旋转键数：
  22
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  90.1
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  E,E-2,5-bis{4-[di(p-anisyl)amino]styryl}-3,4-di(n-butoxy)thiophene 在 silver hexafluoroantimonate 作用下， 以 二氯甲烷 为溶剂， 以78%的产率得到E,E-2,5-bis{4-[di(p-anisyl)amino]styryl}-3,4-di(n-butoxy)thiophene bis(hexafluoroantimonate)
  参考文献：
  名称：

  Isolation and Crystal Structures of Two Singlet Bis(Triarylamine) Dications with Nonquinoidal Geometries

  摘要：

  We report the first structural data for bis(diarylamine) "bipolarons": we have isolated and crystallographically characterized salts of the dications obtained by two-electron oxidation of E-4,4'-bis[di(p-anisyl)amino]stilbene and EE-2,5-bis{4-[di(p-anisyi)amino]styryl}-3,4-di(n-butoxy)thiophene, [1](2+) and [2](2+) respectively. ESR, NMR, and magnetometry suggest both species have singlet ground states. X-ray structures, together with H-1 NMR coupling constants for [2](2+), indicate geometries in which the bond lengths are shifted toward a quinoidal pattern relative to that in the neutral species, but not to a fully quinoidal extent. In particular, the bond-length alternations across the vinylene bridging groups approach zero. DFT calculations with closed-shell singlet configurations reproduce the observed structures well. Our results indicate that singlet species for which one might expect quinoidal geometries (with differences of ca. 0.1 A between formally single and double bonds) on the basis of a limiting valence-bond representation of the structure can, in fact, show structures with significantly different patterns of bond lengths.

  DOI：

  10.1021/ja0541534
• 作为产物：
  描述：

  4-[bis(4-methoxyphenyl)amino]benzyl alcohol 在 potassium tert-butylate 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 E,E-2,5-bis{4-[di(p-anisyl)amino]styryl}-3,4-di(n-butoxy)thiophene
  参考文献：
  名称：

  Isolation and Crystal Structures of Two Singlet Bis(Triarylamine) Dications with Nonquinoidal Geometries

  摘要：

  We report the first structural data for bis(diarylamine) "bipolarons": we have isolated and crystallographically characterized salts of the dications obtained by two-electron oxidation of E-4,4'-bis[di(p-anisyl)amino]stilbene and EE-2,5-bis{4-[di(p-anisyi)amino]styryl}-3,4-di(n-butoxy)thiophene, [1](2+) and [2](2+) respectively. ESR, NMR, and magnetometry suggest both species have singlet ground states. X-ray structures, together with H-1 NMR coupling constants for [2](2+), indicate geometries in which the bond lengths are shifted toward a quinoidal pattern relative to that in the neutral species, but not to a fully quinoidal extent. In particular, the bond-length alternations across the vinylene bridging groups approach zero. DFT calculations with closed-shell singlet configurations reproduce the observed structures well. Our results indicate that singlet species for which one might expect quinoidal geometries (with differences of ca. 0.1 A between formally single and double bonds) on the basis of a limiting valence-bond representation of the structure can, in fact, show structures with significantly different patterns of bond lengths.

  DOI：

  10.1021/ja0541534

文献信息

• High two-photon cross-sections in bis(diarylaminostyryl) chromophores with electron-rich heterocycle and bis(heterocycle)vinylene bridges
  作者：Shijun Zheng、Luca Beverina、Stephen Barlow、Egbert Zojer、Jie Fu、Lazaro A. Padilha、Christian Fink、Ohyun Kwon、Yuanping Yi、Zhigang Shuai、Eric W. Van Stryland、David J. Hagan、Jean-Luc Brédas、Seth R. Marder

  DOI：10.1039/b618265h

  日期：——

  Chromophores in which vinylene units and either pyrrole or dialkoxythiophene groups form the bridge between two diarylaminophenyl groups exhibit two-photon cross-sections of 1000-5000 GM at 600-650 nm.

  亚乙烯基单元与吡咯或二烷氧基噻吩基团形成两个二芳基氨基苯基之间的桥的发色团在600-650 nm处表现出1000-5000 GM的两个光子截面。
• Isolation and Crystal Structures of Two Singlet Bis(Triarylamine) Dications with Nonquinoidal Geometries
  作者：Shijun Zheng、Stephen Barlow、Chad Risko、Tiffany L. Kinnibrugh、Viktor N. Khrustalev、Simon C. Jones、Mikhail Yu. Antipin、Neil M. Tucker、Tatiana V. Timofeeva、Veaceslav Coropceanu、Jean-Luc Brédas、Seth R. Marder

  DOI：10.1021/ja0541534

  日期：2006.2.1

  We report the first structural data for bis(diarylamine) "bipolarons": we have isolated and crystallographically characterized salts of the dications obtained by two-electron oxidation of E-4,4'-bis[di(p-anisyl)amino]stilbene and EE-2,5-bis4-[di(p-anisyi)amino]styryl}-3,4-di(n-butoxy)thiophene, [1](2+) and [2](2+) respectively. ESR, NMR, and magnetometry suggest both species have singlet ground states. X-ray structures, together with H-1 NMR coupling constants for [2](2+), indicate geometries in which the bond lengths are shifted toward a quinoidal pattern relative to that in the neutral species, but not to a fully quinoidal extent. In particular, the bond-length alternations across the vinylene bridging groups approach zero. DFT calculations with closed-shell singlet configurations reproduce the observed structures well. Our results indicate that singlet species for which one might expect quinoidal geometries (with differences of ca. 0.1 A between formally single and double bonds) on the basis of a limiting valence-bond representation of the structure can, in fact, show structures with significantly different patterns of bond lengths.