2,5-bis(diphenylphosphine oxide)thiophene

• 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: 2,5-bis(diphenylphosphine oxide)thiophene
• 英文别名: 2,5-bis(diphenylphosphoryl)thiophene；Thiophene, 2,5-bis(diphenylphosphinyl)-
• 化学式: C₂₈H₂₂O₂P₂S
• 分子量: 484.495
• InChiKey: KYYIRCLYNDIEHT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  62.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,5-bis(diphenylphosphine oxide)thiophene 、 tris(hexafluoroacetylacetonato)europium(III) dihydrate 以 甲醇 为溶剂， 反应 3.0h， 以40%的产率得到[Eu(hfa)₃(dpt)]_n
  参考文献：
  名称：

  发光的（（III）配位拉链与噻吩基桥链接

  摘要：

  新颖铕III的配位聚合物[铕（HFA）3（DPT）] Ñ（DPT：2,5-双（二苯基磷酰基）噻吩）和[铕（HFA）3（dpedot）] Ñ（dpedot：2,5-双（据报道具有氢键结合的拉链结构的二苯基磷酰基）乙撑二氧噻吩）。配位聚合物由Eu III组成离子，六氟乙酰丙酮基配体和基于噻吩的氧化膦桥。单个聚合物链的之字形取向诱导了具有多个分子间相互作用的致密堆积的配位结构的形成，从而导致了300°C以上的热稳定性。由于它们围绕Eu III离子的不对称和低振动配位结构，它们具有很高的固有发射量子产率（约80％）。此外，取代基的特征性替代取向还有助于在固态状态下实现高达80％的极高配体-金属能量转移效率。

  DOI：

  10.1002/anie.201606371
• 作为产物：
  描述：

  (2,5-bis-diphenylphosphino)thiophene 在 双氧水 作用下， 以 氯仿 、 丙酮 为溶剂， 反应 1.0h， 以75%的产率得到2,5-bis(diphenylphosphine oxide)thiophene
  参考文献：
  名称：

  Spectroscopic Study of Phosphine-Substituted Oligothiophenes

  摘要：

  The spectroscopic behaviour (solution and solid-state absorption and emission) of a series of mono(diphenylphosphino) and bis-(diphenylphosphino) alpha-substituted oligothiophenes varying in length from one to three thienyl rings is described. The absorption spectra red-shift with increasing oligomer length, and the spectra of the bisphosphines are red-shifted, relative to the monophosphines that contain the same number of thienyl groups. In solution, emission from the mono- and bithienyl compounds is broad and shows a large Stokes shift, attributed to a planar excited state due to the n --> pi* nature of the excitation. Emission from the terthienyl compounds shows a much smaller Stokes shift and is attributed to a thienyl-based pi --> pi* transition. In the solid state, similar effects are observed in both absorption and emission spectra. Density functional theory (DFT) calculations show that the contribution of the P lone pair to the highest occupied molecular orbital (HOMO) diminishes as the oligomer length increases, supporting the experimental results.

  DOI：

  10.1021/jp047037g

文献信息

• Mn-Catalyzed Electrooxidative Undirected C–H/P–H Cross-Coupling between Aromatics and Diphenyl Phosphine Oxides
  作者：Siyuan Wang、Qilin Xue、Zhipeng Guan、Yayu Ye、Aiwen Lei

  DOI：10.1021/acscatal.1c00549

  日期：2021.4.2

  in C–P bond formation since it requires no pretreatment of substrates. Herein, we reported a Mn-catalyzed electrochemical intermolecular dehydrogenative cross-coupling between aryl C–H and diphenyl phosphine oxides. In undivided cells, a series of phosphorylation or diphosphorylation products could be obtained separately by adjusting the proportion of substrates. A catalytic amount of inexpensive Mn(II)

  C-P键广泛存在于许多生物活性化合物和功能分子中。过渡金属催化的脱氢C–H / P–H交叉偶联在C–P键的形成中起着至关重要的作用，因为它不需要对底物进行预处理。在本文中，我们报道了芳基CH和二苯基氧化膦之间Mn催化的电化学分子间脱氢交叉偶联。在未分裂的细胞中，可以通过调节底物的比例分别获得一系列的磷酸化或二磷酸化产物。使用了催化量的廉价Mn（II）盐，在此过程中不需要外部化学氧化剂。动力学同位素效应实验表明，CH活化不是决定速率的步骤。
• Luminescent Europium(III) Coordination Zippers Linked with Thiophene‐Based Bridges
  作者：Yuichi Hirai、Takayuki Nakanishi、Yuichi Kitagawa、Koji Fushimi、Tomohiro Seki、Hajime Ito、Yasuchika Hasegawa

  DOI：10.1002/anie.201606371

  日期：2016.9.19

  5‐bis(diphenylphosphoryl)thiophene) and [Eu(hfa)3(dpedot)]n (dpedot: 2,5‐bis(diphenylphosphoryl)ethylenedioxythiophene) with hydrogen‐bonded zipper structures are reported. The coordination polymers are composed of EuIII ions, hexafluoroacetylacetonato ligands, and thiophene‐based phosphine oxide bridges. The zig‐zag orientation of single polymer chains induced the formation of densely packed coordination structures

  新颖铕III的配位聚合物[铕（HFA）3（DPT）] Ñ（DPT：2,5-双（二苯基磷酰基）噻吩）和[铕（HFA）3（dpedot）] Ñ（dpedot：2,5-双（据报道具有氢键结合的拉链结构的二苯基磷酰基）乙撑二氧噻吩）。配位聚合物由Eu III组成离子，六氟乙酰丙酮基配体和基于噻吩的氧化膦桥。单个聚合物链的之字形取向诱导了具有多个分子间相互作用的致密堆积的配位结构的形成，从而导致了300°C以上的热稳定性。由于它们围绕Eu III离子的不对称和低振动配位结构，它们具有很高的固有发射量子产率（约80％）。此外，取代基的特征性替代取向还有助于在固态状态下实现高达80％的极高配体-金属能量转移效率。
• Triboluminescence of Lanthanide Coordination Polymers with Face-to-Face Arranged Substituents
  作者：Yuichi Hirai、Takayuki Nakanishi、Yuichi Kitagawa、Koji Fushimi、Tomohiro Seki、Hajime Ito、Yasuchika Hasegawa

  DOI：10.1002/anie.201703638

  日期：2017.6.12

  lanthanideIII coordination polymers with efficient TL and PL properties. They are composed of emission centers (TbIII and EuIII ions), antenna (hexafluoroacetylacetonate=hfa), and bridging ligands (2,5‐bis(diphenylphosphoryl)furan=dpf). The emission color upon grinding (yellow TL) is clearly different from that upon UV irradiation (reddish‐orange PL) in TbIII/EuIII‐mixed coordination polymers [Tb,Eu(hfa)3(dpf)]n

  研磨固体材料时的发光（triboluminescence，TL）长期以来一直是自然科学中令人费解的现象，并且由于其在光学领域的广泛应用也引起了人们的关注。通常认为，TL光谱表现出与光致发光（PL）相似的轮廓，尽管它们来自不同的刺激。在本文中，我们首次使用具有有效TL和PL特性的镧系元素III配位聚合物，首次描述了这两种物理现象之间的大光谱差异。它们由排放中心组成（Tb III和Eu III离子），触角（六氟乙酰丙酮= hfa）和桥连配体（2,5-双（二苯基磷酰基）呋喃= dpf）。在Tb III / Eu III混合配位聚合物[Tb，Eu（hfa）3（dpf）] n（Tb / Eu = 1）。结果直接表明了PL和TL的离散激励过程。
• Spectroscopic Study of Phosphine-Substituted Oligothiophenes
  作者：Tracey L. Stott、Michael O. Wolf

  DOI：10.1021/jp047037g

  日期：2004.12.1

  The spectroscopic behaviour (solution and solid-state absorption and emission) of a series of mono(diphenylphosphino) and bis-(diphenylphosphino) alpha-substituted oligothiophenes varying in length from one to three thienyl rings is described. The absorption spectra red-shift with increasing oligomer length, and the spectra of the bisphosphines are red-shifted, relative to the monophosphines that contain the same number of thienyl groups. In solution, emission from the mono- and bithienyl compounds is broad and shows a large Stokes shift, attributed to a planar excited state due to the n --> pi* nature of the excitation. Emission from the terthienyl compounds shows a much smaller Stokes shift and is attributed to a thienyl-based pi --> pi* transition. In the solid state, similar effects are observed in both absorption and emission spectra. Density functional theory (DFT) calculations show that the contribution of the P lone pair to the highest occupied molecular orbital (HOMO) diminishes as the oligomer length increases, supporting the experimental results.