1-phenyl-2,5-bis(thiophen-2-yl)thioxophosphole | 282728-33-0

• 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: 1-phenyl-2,5-bis(thiophen-2-yl)thioxophosphole
• 英文别名: 1-phenyl-2,5-bis(2-thienyl)thiooxophosphole；2,5-di(2-thienyl)-1-phenylthiooxophosphole；2-(2-Phenyl-2-sulfanylidene-3-thiophen-2-yl-4,5,6,7-tetrahydroisophosphindol-1-yl)thiophene
• CAS: 282728-33-0
• 化学式: C₂₂H₁₉PS₃
• 分子量: 410.565
• InChiKey: AEKIZNXBCZFUPE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  88.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-phenyl-2,5-bis(thiophen-2-yl)thioxophosphole 在 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride 、 potassium carbonate 、 4,4'-二叔丁基-2,2'-二吡啶 作用下， 以 四氢呋喃 、 正己烷 、 氯仿 、 水 、 甲苯 、 乙腈 为溶剂， 反应 72.0h， 生成
  参考文献：
  名称：

  包含磷眼单元的共轭金属超分子聚合物

  摘要：

  A new building block, TPT, composed of the substituted phosphole ring surrounded by two thiophene rings with 2,2':6',2"-terpyridine-4'-yl (tpy) end-groups, is prepared and assembled with metal ions (Co2+, Cu2+, Fe2+, Ni2+, and Zn2+) into metallo-supramolecular polymers (MSPs), and properties of both TPT and the MSPs are compared with those of their counterparts with terthiophene central blocks. A distinct red-shifting of the UV/vis band about by 60-100 nm proves the decrease in the bandgap energy due to replacing the thiophene-2,5-diyl with a phosphole-2,5-diyl central unit, which is due to the lowered aromaticity of phosphole ring compared to the aromaticity of thiophene ring. Assembling TPT with metal ions gives oligomeric chains comprising up to 10 unimeric units in dilute solutions. MSPs with Fe2+ and Ni2+ ion couplers exhibit very slow constitutional dynamics, while those with Cu2+ and Zn2+ ion couplers quite fast constitutional dynamics. A metal ligand charge transfer is observed only for Fe-2+-MSPs, while luminescence is observed only for. Zn2+-MSPs, mainly at an excess of Zn2+ ions, which indicates a positive effect of the end-capping of MSP chains with these ions.

  DOI：

  10.1021/acs.organomet.6b00822
• 作为产物：
  描述：

  P-苯基-亚膦二溴化物 在 正丁基锂 、 二氯二茂锆 、 sulfur 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 53.0h， 生成 1-phenyl-2,5-bis(thiophen-2-yl)thioxophosphole
  参考文献：
  名称：

  Phosphole-Containing π-Conjugated Systems: From Model Molecules to Polymer Films on Electrodes

  摘要：

  Two series of 2.5-dipyridyl and 2.5-dithienylphosphole derivatives containing sigma (3)- or sigma (4)-P atoms were prepared. and their optical (UV/Vis absorption, fluorescence spectra) and electrochemical properties were systematically evaluated. These physical properties depend mainly on the natures of the 2.5-substituents and of the phosphorus moiety, and they revealed that these compounds contain extended pi- conjugated systems. Structure -property relationships were established on the basis of these experimental data and ab initio calculations on the parent molecules. The limited aromatic character and low-lying LUMO of the phosphole ring appear to be crucial for achieving a highly delocalised pi system. Electrooxidation of 2,5-dithienylphosphole derivatives affords electroactive films with low optical band gaps. As observed for the corresponding monomers, the optical and electrochemical properties of the polymers can be varied over a wide range by modifying the nature of the phosphorus moiety.

  DOI：

  10.1002/1521-3765(20011001)7:19<4222::aid-chem4222>3.0.co;2-3

文献信息

• An aromatic–antiaromatic switch in P-heteroles. A small change in delocalisation makes a big reactivity difference
  作者：László Nyulászi、Oldamur Hollóczki、Christophe Lescop、Muriel Hissler、Régis Réau

  DOI：10.1039/b516836h

  日期：——

  The low aromaticity of phosphole can be switched to low antiaromaticity by oxidizing the phosphorus atom. This subtle change in the mode of delocalisation alters substantially the chemical behaviour of these heteroles.

  通过氧化磷原子，可以将磷环的低芳香性转变为低反芳香性。这种分散模式的微妙变化大大改变了这些杂环的化学特性。
• Electropolymerization of π-Conjugated Oligomers Containing Phosphole Cores and Terminal Thienyl Moieties: Optical and Electronic Properties
  作者：Caroline Hay、Cédric Fischmeister、Muriel Hissler、Loic Toupet、Régis Réau

  DOI：10.1002/(sici)1521-3773(20000515)39:10<1812::aid-anie1812>3.0.co;2-d

  日期：2000.5.15
• Phosphole-Containing π-Conjugated Systems: From Model Molecules to Polymer Films on Electrodes
  作者：Caroline Hay、Muriel Hissler、Cédric Fischmeister、Joëlle Rault-Berthelot、Loïc Toupet、László Nyulászi、Régis Réau

  DOI：10.1002/1521-3765(20011001)7:19<4222::aid-chem4222>3.0.co;2-3

  日期：2001.10.1

  Two series of 2.5-dipyridyl and 2.5-dithienylphosphole derivatives containing sigma (3)- or sigma (4)-P atoms were prepared. and their optical (UV/Vis absorption, fluorescence spectra) and electrochemical properties were systematically evaluated. These physical properties depend mainly on the natures of the 2.5-substituents and of the phosphorus moiety, and they revealed that these compounds contain extended pi- conjugated systems. Structure -property relationships were established on the basis of these experimental data and ab initio calculations on the parent molecules. The limited aromatic character and low-lying LUMO of the phosphole ring appear to be crucial for achieving a highly delocalised pi system. Electrooxidation of 2,5-dithienylphosphole derivatives affords electroactive films with low optical band gaps. As observed for the corresponding monomers, the optical and electrochemical properties of the polymers can be varied over a wide range by modifying the nature of the phosphorus moiety.
• Conjugated Metallo-Supramolecular Polymers Containing a Phosphole Unit
  作者：Tereza Vitvarová、Jan Svoboda、Muriel Hissler、Jiří Vohlídal

  DOI：10.1021/acs.organomet.6b00822

  日期：2017.2.27

  A new building block, TPT, composed of the substituted phosphole ring surrounded by two thiophene rings with 2,2':6',2"-terpyridine-4'-yl (tpy) end-groups, is prepared and assembled with metal ions (Co2+, Cu2+, Fe2+, Ni2+, and Zn2+) into metallo-supramolecular polymers (MSPs), and properties of both TPT and the MSPs are compared with those of their counterparts with terthiophene central blocks. A distinct red-shifting of the UV/vis band about by 60-100 nm proves the decrease in the bandgap energy due to replacing the thiophene-2,5-diyl with a phosphole-2,5-diyl central unit, which is due to the lowered aromaticity of phosphole ring compared to the aromaticity of thiophene ring. Assembling TPT with metal ions gives oligomeric chains comprising up to 10 unimeric units in dilute solutions. MSPs with Fe2+ and Ni2+ ion couplers exhibit very slow constitutional dynamics, while those with Cu2+ and Zn2+ ion couplers quite fast constitutional dynamics. A metal ligand charge transfer is observed only for Fe-2+-MSPs, while luminescence is observed only for. Zn2+-MSPs, mainly at an excess of Zn2+ ions, which indicates a positive effect of the end-capping of MSP chains with these ions.