diphenyl(2,2'-bithienyl-5-yl)phosphine | 409093-85-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 双噻吩和低聚噻吩
• 英文名称: diphenyl(2,2'-bithienyl-5-yl)phosphine
• 英文别名: 2-diphenylphosphino-5,2'-bithiophene；5-(diphenylphosphino)-2,2'-bithiophene；2T-PPh2；PT2；Diphenyl-(5-thiophen-2-ylthiophen-2-yl)phosphane
• CAS: 409093-85-2
• 化学式: C₂₀H₁₅PS₂
• 分子量: 350.445
• InChiKey: BKWAMYRZTBAZAD-UHFFFAOYSA-N

物化性质

• 沸点：
  471.7±35.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  diphenyl(2,2'-bithienyl-5-yl)phosphine 在 sodium tetrahydroborate 、 双氧水 、 碘 、 potassium carbonate 、 三氯氧磷 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 1,2-二氯乙烷 、 丙酮 为溶剂， 反应 56.0h， 生成 methyl 5-(diphenyloxophosphino)-2,2'-bithiophene-5'-carboxylate
  参考文献：
  名称：

  Syntheses, X-ray Crystal Structures, and Optical, Fluorescence, and Nonlinear Optical Characterizations of Diphenylphosphino-Substituted Bithiophenes

  摘要：

  A series of bithiophene derivatives that are either symmetrically disubstituted with two Ph-2(X)P groups (X = O, S, Se) or monosubstituted with one Ph-2(X)P group (X = O, S, Se) and an organic functional group (H, CHO, CH2OH, CO2Me) have been synthesized. The X-ray crystal structures of Ph-2(Se)P(C4H2S)(2)P(Se)Ph-2, Ph-2(O)P(C4H2S)(2)H, Ph-2(S)P(C4H2S)(2)H, and Ph-2(O)P(C4H2S)(2)CH2OH exhibit very different solid-state structures depending on the type of intermolecular pi-pi interactions that occur. The compounds have been characterized by electronic absorption and fluorescence studies. Of particular interest is that the quantum yields of Ph-2(O)P(C4H2S)(2)H, Ph-2(O)P(C4H2S)(2)P(O)Ph-2, Ph-2(O)P(C4H2S)(2)CO2Me, and Ph-2(O)P(C4H2S)(2)CH2OH are significantly larger than that of bithiophene (factors of 13, 14, 14, and 2,2, respectively). This behavior is quite different from that of analogously substituted terthiophenes in which substitution results in only modest increases in the quantum yields over that of terthiophene (factors of 0.94, 2.7, 1.3, and 1.5, respectively). DFT studies of the emission process suggest that modifying the Ph-2(X)P group affects both the fluorescence and nonradiative rate constants while modifications of the organic substituents primarily affect the nonradiative rate constants. The higher quantum yields of the substituted bithiophenes make them promising for application in organic light-emitting devices (OLED). The optical power limiting (OPL) performances of these Ph-2(X)P-substituted bithiophenes were evaluated by nonlinear transmission measurements in the violet-blue spectral region (430-480 nm) with picosecond laser pulses. The OPL performances are enhanced by heavier X groups and when by higher solubilities. Saturated chloroform solutions of Ph-2(O)P(C4H2S)(2)H and Ph-2(S)P(C4H2S)(2)H exhibit significantly stronger nonlinear absorption than any previously reported compounds and are promising candidates for use in broadband optical power limiters.

  DOI：

  10.1021/ic201309k
• 作为产物：
  描述：

  二苯基氯化膦 在 magnesium 作用下， 以 乙醚 为溶剂， 反应 15.0h， 生成 diphenyl(2,2'-bithienyl-5-yl)phosphine
  参考文献：
  名称：

  Field, John S.; Haines, Raymond J.; Lakoba, Elena I., Journal of the Chemical Society. Perkin Transactions 1 (2001), 2001, # 24, p. 3352 - 3360

  摘要：

  DOI：

文献信息

• Diverse C–P Cross-Couplings of Arylsulfonium Salts with Diarylphosphines via Selective C–S Bond Cleavage
  作者：Yun Ye、Jie Zhu、Yinhua Huang

  DOI：10.1021/acs.orglett.1c00748

  日期：2021.3.19

  Diverse C–P cross-couplings of arylthianthrenium salts with diarylphosphines producing various triarylphosphines via highly selective C–S bond cleavage are reported. In the absence of catalyst, the reaction of arylthianthrenium salts with diarylphosphines undergoes phosphinative ring opening exclusively via the cleavage of an endocyclic C–S bond of a thianthrene skeleton. The use of a palladacycle

  据报道，芳基噻吨鎓盐与二芳基膦通过不同的C–P交叉偶联，可通过高选择性的C–S键裂解产生各种三芳基膦。在没有催化剂的情况下，芳基噻吨鎓盐与二芳基膦的反应仅通过裂解噻吩骨架的内环C–S键进行膦化开环。在其他条件相同的情况下使用Palladacycle催化剂，则可以通过裂解环外C-S键以更高的速度进行磷酸化反应。
• Synthesis, linear and nonlinear optical properties of phosphonato-substituted bithiophenes derived from 2,2′-biphenol
  作者：Jason L. Freeman、Qun Zhao、Yuanli Zhang、Jianwei Wang、Christopher M. Lawson、Gary M. Gray

  DOI：10.1039/c3dt51499d

  日期：——

  Two new series of phosphonato-substituted bithiophenes, BpP(X)(C4H2S)2H and BpP(X)(C4H2S)2P(X)Bp (Bp = 2,2′-C12H8O2, X = O, S, Se), have been synthesized and characterized using linear absorption and emission spectra, and third-order nonlinear absorption measurements at 430 nm with 27 ps laser pulses. The compounds were synthesized in three steps: (1) reacting lithiated bithiophene with (Et2N)2PCl; (2) reacting the product from the first step with biphenol; and (3) reacting the product from the second step with the appropriate chalcogen. The X-ray crystal structures of two of the compounds, BpP(O)(C4H2S)2P(O)Bp and BpP(Se)(C4H2S)2P(Se)Bp, are reported and show a number of intermolecular π–π interactions. The linear absorption spectra, emission spectra, and emission quantum yields show distinct trends with respect to the chalcogen and the number of phosphorus substituents attached to the 2,2′-bithiophene ring. The compounds show emission maxima at wavelengths ranging from 380–400 nm and, BpP(S)(C4H2S)2H shows a 23-fold increase in fluorescence quantum yield relative to that of 2,2′-bithiophene. Fluorescence lifetimes and radiative and non-radiative decay rate constants for the first singlet excited state have been extracted from the quantum yields using time-dependent DFT calculations. Nonlinear transmission measurements indicate that all of the compounds show nonlinear absorption at 430 nm with 27 ps laser pulses in spite of their low solubilities. Notably, the nonlinear absorption threshold of a 0.16 mol L−1 CH2Cl2 solution of BpP(Se)(C4H2S)2H is 0.9 J cm−2. The excellent emission quantum yields and good nonlinear absorptions make these compounds promising candidates for optical power limiting applications and as host materials for violet-blue organic light emitting diodes.

  合成并表征了两种新的磷酸酯取代的双噻吩系列化合物BpP(X)(C4H2S)2H和BpP(X)(C4H2S)2P(X)Bp（Bp = 2,2'-C12H8O2，X = O，S，Se），使用线性吸收和发射光谱，以及在430 nm波长下利用27 ps激光脉冲进行的三阶非线性吸收测量。这些化合物的合成分为三个步骤：（1）将锂化的双噻吩与(Et2N)2PCl反应；（2）将第一步的产物与联苯酚反应；（3）将第二步的产物与相应的化学元素反应。报告了两种化合物BpP(O)(C4H2S)2P(O)Bp和BpP(Se)(C4H2S)2P(Se)Bp的X射线晶体结构，显示了一些分子间的π–π相互作用。线性吸收光谱、发射光谱和发射量子产率显示出相对于化学元素及附着于2,2'-双噻吩环的磷替代体数量的明显趋势。这些化合物在380–400 nm波长范围内显示出发射最大值，其中BpP(S)(C4H2S)2H的荧光量子产率相对于2,2'-双噻吩增加了23倍。通过时间相关的密度泛函理论计算，从量子产率中提取了第一激发单态的荧光寿命和辐射与非辐射衰减速率常数。非线性传输测量显示，尽管这些化合物的溶解度较低，但在430 nm波长下使用27 ps激光脉冲时均表现出非线性吸收。值得注意的是，0.16 mol L⁻¹ CH2Cl2溶液中BpP(Se)(C4H2S)2H的非线性吸收阈值为0.9 J cm⁻²。优异的发射量子产率和良好的非线性吸收使这些化合物成为光功率限制应用和紫蓝色有机发光二极管的宿主材料的有希望的候选者。
• Synthesis and Characterization of Cyclic Oligomeric [<i>cis</i>-Mo(CO)₄(Ph₂P(C₄H₂S)₂PPh₂)]<i>_n</i> and Model Complexes for the Edge and Corners in the Cyclic Oligomer
  作者：R. Dustan Myrex、Clark S. Colbert、Gary M. Gray、Christina H. Duffey

  DOI：10.1021/om030595h

  日期：2004.2.1

  Conducting organometallic polymers are an interesting class of materials because they combine the electronic properties of metals with the simpler processing requirements of organic polymers. In an approach to incorporating poly(thiophene) segments into controlled three-dimensional environments, we have synthesized 5,5‘-bis(diphenylphosphino)-2,2‘-bithiophene, Ph2P(C4H2S)2PPh2, and have reacted this

  导电有机金属聚合物是一类有趣的材料，因为它们将金属的电子特性与有机聚合物的更简单加工要求结合在一起。在将聚噻吩链段纳入受控的三维环境的一种方法中，我们合成了5,5'-双（二苯基膦基）-2,2'-联噻吩，Ph 2 P（C 4 H 2 S）2 PPh 2，并使该配体与Mo（CO）4（nbd）以1：1的比例反应。该反应的产物是环状低聚物，这通过IR光谱中仅存在顺式-Mo（CO）4吸收以及在该光谱中不存在游离膦的共振来表明。31 P 1 H} NMR谱。聚合物在THF中的尺寸排阻色谱法测得该聚合物的M n n值为6.0×10 3，M w值为9.7×10 3。为了更好地理解聚合物的结构特征，对边缘Mo（CO）5（Ph 2 P（C 4 H 2 S）2 PPh 2）Mo（CO）5和边角顺式-Mo（ CO）4（Ph 2 P（C 4 H 2 S）2 H）2和顺-Mo（CO）4（PH 2 PC 4 ħ 2
• Intermolecular interactions and electronic properties in phosphino-(oligothiophene) palladium(II) and platinum(II) complexes
  作者：Tracey L Stott、Michael O Wolf、Brian O Patrick

  DOI：10.1139/v07-033

  日期：2007.5.1

  of Pt(II) and Pd(II) complexes containing diphenylphosphino-substituted oligothiophene ligands ranging from 1 to 3 thiophene rings in length have been prepared. Crystal structures of four of these complexes were determined via single X-ray crystal diffraction and the solid-state packing arrangements found to vary with both the metal and the thiophene-containing ligand. In some cases, π-stacking between

  已经制备了一系列含有二苯基膦取代的低聚噻吩配体的 Pt(II) 和 Pd(II) 配合物，长度范围为 1 到 3 个噻吩环。其中四种配合物的晶体结构是通过单 X 射线晶体衍射确定的，并且发现固态堆积排列随金属和含噻吩的配体而变化。在某些情况下，发现低聚噻吩配体的噻吩环之间存在 π 堆积。报道了这些配合物的溶液和固态吸收光谱。关键词：低聚噻吩，金属配合物，结构特性，电子光谱。
• Structural and Electronic Properties of Phosphino(oligothiophene) Gold(I) Complexes
  作者：Tracey L. Stott、Michael O. Wolf、Brian O. Patrick

  DOI：10.1021/ic0493200

  日期：2005.2.1

  A series of gold(I) complexes containing phosphino(oligothiophene) ligands of varying conjugation length has been prepared. Solid state crystal structures of (PT3)AuCl (PT3 = 5-diphenylphosphino-2,2':5',2"-terthiophene) and AuCl-(PTP)AuCl (PTP = 2,5-diphenylphosphinothiophene) have been obtained. The complex AuCl(PTP)AuCl crystallizes as a dimer with two intermolecular Au-Au contacts. Variable temperature NMR spectroscopy is used to demonstrate the presence of aurophilic interactions in solution for Aul(PTP)Aul. Dual emission is observed for AuCl(PTP)AuCl in solution and is attributed to emission from both monomer and dimer. In the solid state, dimer emission is dominant. The iodo analogue, Aul(PTP)Aul, shows only low energy dimer emission in both solution and the solid state. Compounds in which the ligands contain longer bridges (either bithienyl or terthienyl) show absorption and emission bands due to the pi-pi* transition only, both in solution and the solid state.