4,12-Diethynyl-8-phenyl-3,13-dithia-8-phosphatricyclo[8.3.0.02,6]trideca-1(10),2(6),4,11-tetraene-7,9-dione | 1417639-17-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: 4,12-Diethynyl-8-phenyl-3,13-dithia-8-phosphatricyclo[8.3.0.02,6]trideca-1(10),2(6),4,11-tetraene-7,9-dione
• 英文别名: 4,12-diethynyl-8-phenyl-3,13-dithia-8-phosphatricyclo[8.3.0.02,6]trideca-1(10),2(6),4,11-tetraene-7,9-dione
• CAS: 1417639-17-8
• 化学式: C₂₀H₉O₂PS₂
• 分子量: 376.396
• InChiKey: BGDUNIARZNFYMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  90.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,12-Diethynyl-8-phenyl-3,13-dithia-8-phosphatricyclo[8.3.0.02,6]trideca-1(10),2(6),4,11-tetraene-7,9-dione 、 1-叠氮基-4-甲氧基苯 在 Cu(PPh3)3Br 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 生成 4,12-Bis[1-(4-methoxyphenyl)triazol-4-yl]-8-phenyl-3,13-dithia-8-phosphatricyclo[8.3.0.02,6]trideca-1(10),2(6),4,11-tetraene-7,9-dione
  参考文献：
  名称：

  Dithieno[3,2-c:2′,3′-e]-2,7-diketophosphepin: A Unique Building Block for Multifunctional π-Conjugated Materials

  摘要：

  A series of conjugated materials based on the new dithieno[3,2-c:2',3'-e]-2,7-diketophosphepin (DTDKP) building block have been studied for the first time. Theoretical calculations predict DTDKP to be a better electron acceptor than the well-known dithienophosphole and the nitrogen analogue, bithiopheneimide. Cyclic voltammetry studies revealed two reduction processes that support their promising electron-acceptor properties, and modification of the P center with O or gold(I) further reduced the LUMO energy to ca. -3.6 eV. Expansion of the DTDKP core with various aromatic moieties has been realized using the Huisgen alkynyl click reaction, resulting in altered optical and electrochemical properties with compounds showing a high-energy absorption band at ca. 270-290 nm and a low-energy band at ca. 390-460 nm. The acceptor character of the DTDKP core was demonstrated by a red shift following the electron-donating strength of the appended aromatic moiety. Intriguing white-light emission from just a single species with the CIE coordinates of (0.33, 0.34) was observed for some of the extended species as the result of an unexpected dual-emission behavior. The high-energy emission in the blue-to-green region and the low-energy emission in the orange-to-red region are attributed to a pi* -> pi transition of the DTDKP core and charge transfer from the triazole moiety to DTDKP, respectively. Apart from tuning of the molecular properties, this novel building block has also been applied in a self-assembled organogel, which exhibited pronounced luminescence. Scanning electron microscopy confirmed that the gel self-assembled by forming a network of entangled ID fibrous structures on the micrometer scale.

  DOI：

  10.1021/ja310680x
• 作为产物：
  描述：

  3,3',5,5'-四溴-2,2'-联噻吩 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 正丁基锂 、 草酰氯 、 二异丙胺 、 N,N-二甲基甲酰胺 、 三苯基膦 、 potassium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 38.5h， 生成 4,12-Diethynyl-8-phenyl-3,13-dithia-8-phosphatricyclo[8.3.0.02,6]trideca-1(10),2(6),4,11-tetraene-7,9-dione
  参考文献：
  名称：

  Dithieno[3,2-c:2′,3′-e]-2,7-diketophosphepin: A Unique Building Block for Multifunctional π-Conjugated Materials

  摘要：

  A series of conjugated materials based on the new dithieno[3,2-c:2',3'-e]-2,7-diketophosphepin (DTDKP) building block have been studied for the first time. Theoretical calculations predict DTDKP to be a better electron acceptor than the well-known dithienophosphole and the nitrogen analogue, bithiopheneimide. Cyclic voltammetry studies revealed two reduction processes that support their promising electron-acceptor properties, and modification of the P center with O or gold(I) further reduced the LUMO energy to ca. -3.6 eV. Expansion of the DTDKP core with various aromatic moieties has been realized using the Huisgen alkynyl click reaction, resulting in altered optical and electrochemical properties with compounds showing a high-energy absorption band at ca. 270-290 nm and a low-energy band at ca. 390-460 nm. The acceptor character of the DTDKP core was demonstrated by a red shift following the electron-donating strength of the appended aromatic moiety. Intriguing white-light emission from just a single species with the CIE coordinates of (0.33, 0.34) was observed for some of the extended species as the result of an unexpected dual-emission behavior. The high-energy emission in the blue-to-green region and the low-energy emission in the orange-to-red region are attributed to a pi* -> pi transition of the DTDKP core and charge transfer from the triazole moiety to DTDKP, respectively. Apart from tuning of the molecular properties, this novel building block has also been applied in a self-assembled organogel, which exhibited pronounced luminescence. Scanning electron microscopy confirmed that the gel self-assembled by forming a network of entangled ID fibrous structures on the micrometer scale.

  DOI：

  10.1021/ja310680x

文献信息

• Synthesis and Properties of a Dicationic π-Extended Dithieno[3,2-<i>c</i>:2′,3′-<i>e</i>]-2,7-diketophosphepin
  作者：Xiaoming He、Thomas Baumgartner

  DOI：10.1021/om400991a

  日期：2013.12.23

  Methylation of the triazole units of a π-extended, fluorescent dithieno[3,2-c:2′,3′-e]-2,7-diketophosphepin gives rise to a N,N-dimethylated species that shows considerably blue-shifted absorption and emission wavelengths, as well as two reversible and remarkably low reduction steps at Ered = −1.12 and −1.39 V that underline its improved electron-acceptor features. The observed properties are the result

  的π延长，荧光灯的二噻吩并三唑单元的甲基化[3,2- c ^：2'，3'- ë ] -2,7- diketophosphepin产生了N，N-二甲基化的物种，显示了显着蓝移吸收和发射波长，以及在两个可逆和相当低的还原步骤Ê红= -1.12和-1.39信息v下划线其改进电子受体的功能。所观察到的性质是通过支架的简单触发甲基大大改变电子以及结构特征的结果。
• Dithieno[3,2-<i>c</i>:2′,3′-<i>e</i>]-2,7-diketophosphepin: A Unique Building Block for Multifunctional π-Conjugated Materials
  作者：Xiaoming He、Javier Borau-Garcia、Alva Y. Y. Woo、Simon Trudel、Thomas Baumgartner

  DOI：10.1021/ja310680x

  日期：2013.1.23

  A series of conjugated materials based on the new dithieno[3,2-c:2',3'-e]-2,7-diketophosphepin (DTDKP) building block have been studied for the first time. Theoretical calculations predict DTDKP to be a better electron acceptor than the well-known dithienophosphole and the nitrogen analogue, bithiopheneimide. Cyclic voltammetry studies revealed two reduction processes that support their promising electron-acceptor properties, and modification of the P center with O or gold(I) further reduced the LUMO energy to ca. -3.6 eV. Expansion of the DTDKP core with various aromatic moieties has been realized using the Huisgen alkynyl click reaction, resulting in altered optical and electrochemical properties with compounds showing a high-energy absorption band at ca. 270-290 nm and a low-energy band at ca. 390-460 nm. The acceptor character of the DTDKP core was demonstrated by a red shift following the electron-donating strength of the appended aromatic moiety. Intriguing white-light emission from just a single species with the CIE coordinates of (0.33, 0.34) was observed for some of the extended species as the result of an unexpected dual-emission behavior. The high-energy emission in the blue-to-green region and the low-energy emission in the orange-to-red region are attributed to a pi* -> pi transition of the DTDKP core and charge transfer from the triazole moiety to DTDKP, respectively. Apart from tuning of the molecular properties, this novel building block has also been applied in a self-assembled organogel, which exhibited pronounced luminescence. Scanning electron microscopy confirmed that the gel self-assembled by forming a network of entangled ID fibrous structures on the micrometer scale.