4,4''-双(二苯基磷酰)-1,1':4',1''-三苯基 | 17249-04-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 4,4''-双(二苯基磷酰)-1,1':4',1''-三苯基
• 中文别名: 4,4-(双二苯基膦)三联苯
• 英文名称: PPh₂(C₆H₄)₃PPh₂
• 英文别名: 4,4'-Bis-(diphenylphosphino)-p-terphenyl；4,4'-bis(diphenylphosphino)-terphenyl；4,4''-Ph2PC6H4C6H4C6H4PPh2；[4-[4-(4-Diphenylphosphanylphenyl)phenyl]phenyl]-diphenylphosphane
• CAS: 17249-04-6
• 化学式: C₄₂H₃₂P₂
• 分子量: 598.664
• InChiKey: KAVVIXDPYHHILF-UHFFFAOYSA-N

物化性质

• 沸点：
  702.7±53.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.5
• 重原子数：
  44
• 可旋转键数：
  8
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  4,4''-双(二苯基磷酰)-1,1':4',1''-三苯基 、 Gold(I)-phenylmercaptid 以 二氯甲烷 为溶剂， 以94%的产率得到[(Au(phenylthiolato))2(4,4''-Ph2PC6H4C6H4C6H4PPh2)]
  参考文献：
  名称：

  合成，结构表征，光物理性质和金的理论分析（我）硫醇-膦配合物†

  摘要：

  一系列化学计量的发光双核中性配合物[（AuSPh）2（PPh 2-（C 6 H 4）n -PPh 2）]（n = 1，2，3）以及它们的四核阳离子衍生物[（Au 2报道了SPh）2（PPh 2-（C 6 H 4）n -PPh 2）2 ]（PF 6）2。X射线研究已阐明了它们的晶体结构。这些研究表明，对于双核物种，只有当n= 1分子表现出分子间亲香相互作用。由于通过Au⋯Au相互作用形成聚集体，因此四核物种均未以分子形式结晶。发光的起源已经通过计算研究进行了分析，表明存在或不存在亲嗜性相互作用不影响发光行为，并且涉及硫醇盐和二膦的配体内电荷转移过程是造成发光的原因。结果与硫醇盐-金电荷转移过程相反，后者主导了硫醇酸金化合物的光物理性质，并揭示了亚苯基间隔基对这些化合物的发射行为的影响。

  DOI：

  10.1039/c1dt10437c
• 作为产物：
  描述：

  Sulfuric acid mono-(4-sulfooxy-[1,1';4',1'']terphenyl-4''-yl) ester 、 二苯基膦酸锂 生成 4,4''-双(二苯基磷酰)-1,1':4',1''-三苯基
  参考文献：
  名称：

  Zum Problem der Bandenzuordnung in UV-Spektren terti�rer Phosphine

  摘要：

  DOI：

  10.1007/bf00908988

文献信息

• Synthesis, Structure, and Photophysical Properties of the Di- and Trinuclear Phosphine-Diimine Complexes of Copper(I)
  作者：Ekaterina S. Smirnova、Anna A. Melekhova、Vladislav V. Gurzhiy、Stanislav I. Selivanov、Dmitrii V. Krupenya、Igor O. Koshevoy、Sergey P. Tunik

  DOI：10.1002/zaac.201100472

  日期：2012.2

  the corresponding di- or trinuclear copper(I) acetonitrile-phosphine complexes 1–5. Substitution of the labile acetonitrile groups with chelating aromatic diimines – 2, 2′-bipyridine (bpy), 1, 10-phenanthroline (phen), 5, 6-dimethyl-1, 10-phenanthroline (dmp), 5, 6-dibromo-1, 10-phenanthroline (phenBr2) – gives the corresponding substituted compounds 6–16. In all complexes 1–16 each central CuI atom

  [Cu(NCMe)4]+ 与化学计量的二膦 R2P–(C6H4)n–PR2 (R = NC4H4, n = 1; R = Ph, n = 1, 2, 3) 或三膦 1 的反应, 3, 5-(PPh2– –)3–C6H3 配体得到相应的双核或三核铜 (I) 乙腈-膦配合物 1-5。用螯合芳族二亚胺取代不稳定的乙腈基团 – 2, 2'-联吡啶 (bpy), 1, 10-菲咯啉 (phen), 5, 6-二甲基-1, 10-菲咯啉 (dmp), 5, 6-二溴-1, 10-菲咯啉 (phenBr2) – 得到相应的取代化合物 6-16。在所有配合物 1-16 中，每个中心 CuI 原子都有四面体构型，由两个 N-和两个 P-供体基团完成。使用元素分析、ESI-MS、X 射线晶体学和 NMR 光谱对获得的化合物进行表征。所有膦-二亚胺化合物 6-16 在室温下在二氯甲烷溶液和固态（λex =
• Emission tuning in dinuclear gold complexes with diphosphanes containing alkyne and/or oligophenylene spacers
  作者：Jéssica Cámara、Olga Crespo、M. Concepción Gimeno、Igor O. Koshevoy、Antonio Laguna、Isaura Ospino、Ekaterina S. Smirnova、Sergey P. Tunik

  DOI：10.1039/c2dt31019h

  日期：——

  Reaction of the diphosphanes P∼P [PPh2(C6H4)nPPh2 (n = 1–5) and PPh2CC(C6H4)CCPPh2] with [AuX(tht)] (X = Cl, C6F5) in a 1 : 2 molar ratio affords dinuclear luminescent complexes of formula [(AuX)2(P∼P)]. The photoemissive properties of these complexes are mainly controlled by the presence of the diphosphane ligand, specifically by the phenylene spacers of the diphosphanes. At room temperature fluorescent (IL) processes dominate the emissions, both in solution and in the solid state. Frozen solutions or solids at 77 K display dual emissions or only one emission attributed to ligand to ligand charge transfer (LL′CT) transitions from the auxiliary ligand (L) to phenylene spacers of the diphosphane (L′).

  双膦 P∼P [PPh2(C6H4)nPPh2 (n = 1–5) 和 PPh2CC( )CCPPh2] 与 [AuX(tht)] (X = Cl, C6F5) 以 1 : 2 摩尔比反应，得到双核式[(AuX)2(P∼P)]的发光配合物。这些配合物的光电发射性质主要由二膦配体的存在控制，特别是由二膦的亚苯基间隔基控制。在室温下，荧光 (IL) 过程在溶液和固态的排放中占主导地位。 77 K 下的冷冻溶液或固体显示双重发射或仅一种发射，归因于从辅助配体 (L) 到二膦 (L') 的亚苯基间隔基的配体到配体电荷转移 (LL'CT) 跃迁。
• Supramolecular Luminescent Gold(I)−Copper(I) Complexes: Self-Assembly of the Au_<i>x</i>Cu_<i>y</i> Clusters inside the [Au₃(diphosphine)₃]³⁺ Triangles
  作者：Igor O. Koshevoy、Antti J. Karttunen、Sergey P. Tunik、Matti Haukka、Stanislav I. Selivanov、Alexei S. Melnikov、Pavel Yu. Serdobintsev、Mikhail A. Khodorkovskiy、Tapani A. Pakkanen

  DOI：10.1021/ic801073k

  日期：2008.10.20

  diphosphino-alkynyl gold complexes (PhC2Au)PPh2(C6H4)(n)PPh2(AuC2Ph) (n = 1, 2, 3) with Cu(+) lead to formation of the heterometallic aggregates, the composition of which may be described by a general formula [Au(x)Cu(y)(C2Ph)2x}Au3PPh2(C6H4)(n)PPh2}3](3+(y-x)) (n = 1, 2, 3; x = (n + 1)(n + 2)/2; y = n(n + 1)). These compounds display very similar structural patterns and consist of the [Au(x)Cu(y)(C2Ph)2x](y-x)

  二膦基炔基金配合物（PhC2Au）PPh2（C6H4）（n）PPh2（AuC2Ph）（n = 1，2，3）与Cu（+）之间的反应导致形成杂金属聚集体，其组成可能为用通式[Au（x）Cu（y）（C2Ph）2x} Au3 PPh2（ ）（n）PPh2} 3]描述[3+（yx））（n = 1，2，3; x =（n + 1）（n + 2）/ 2; y = n（n + 1））。这些化合物显示出非常相似的结构模式，并且由[Au3（diphosphine）3]（3+）三角形中“包裹”的[Au（x）Cu（y）（C2Ph）2x]（yx）炔基簇组成。对n = 1的配合物进行了结晶学和光谱表征，较大的配合物（n = 2，3）通过NMR光谱学进行了详细研究。已经研究了它们的发光行为，并且检测到具有最大量子产率为0.92（n = 1）的非常有效的发射。光物理实验表明，聚集体尺寸的增加导致光稳定性和光效率的
• Polynuclear cage-like Au(<scp>i</scp>) phosphane complexes based on a S²⁻ template: observation of multiple luminescence in coordinated polyaromatic systems
  作者：Julia R. Shakirova、Elena V. Grachova、Vladimir V. Sizov、Galina L. Starova、Igor O. Koshevoy、Alexey S. Melnikov、M. Concepción Gimeno、Antonio Laguna、Sergey P. Tunik

  DOI：10.1039/c6dt04126d

  日期：——

  rational approach to the synthesis of cage-like compounds has been realized to build a new family of sulfido-phosphane Au(I) polynuclear complexes. Ditopic phosphane ligands with an extended aromatic system were used to obtain cage compounds with a clearly determined geometry. Au(I) complexes have been fully characterised in solution using spectroscopy methods, and DFT optimisation of the molecular structure

  已经实现了合成笼状化合物的合理方法，以建立新的硫代膦Au（I）多核配合物家族。具有扩展的芳族体系的对位膦配体用于获得具有明确确定的几何形状的笼状化合物。Au（I）配合物已在使用光谱法的溶液中得到了充分表征，并且分子结构的DFT优化为所建议的结构模式提供了更多论据。所获得的所有络合物在溶液中均处于固态发光，并以两个磷光带和一个荧光带的不寻常组合显示出多种发射。DFT计算表明，多种排放主要由1确定。IL和金属干扰了3个IL跃迁。单线态和三线态发射成分的比率取决于配体发色中心与Au（I）之间的距离。
• Tuning the Energy Emission from Violet to Yellow with Bidentate Phosphine Gold(III) Complexes
  作者：Vanesa Fernández-Moreira、Jéssica Cámara、Ekaterina S. Smirnova、Igor O. Koshevoy、Antonio Laguna、Sergey P. Tunik、M. Carmen Blanco、M. Concepción Gimeno

  DOI：10.1021/acs.organomet.6b00135

  日期：2016.4.25

  The synthesis and characterization of luminescent gold(III) compounds, obtained by coordination of the metal center to different phosphines, is described. To avoid deactivation of luminescence by the presence of low-energy d-d ligand field states in the gold(III) center, the ligands bonded to the metallic center have been carefully chosen, among which we used bidentate phosphines with different numbers of phenylene or alkynyl-phenylene spacers and pentafluorophenyl groups. The reaction of [Au(C6F5)(3)(tht)] (tht = tetrahydrothiophene) with the corresponding diphosphines gave the complexes [Au(C6F5)(3)}(2)(1,4PPh(2)(C6H4) nPPh2)] (n = 1-3) and [Au(C6F5)(3)}(2)(PPh2C equivalent to C(C6H4)(n)C equivalent to CPPh2)] (n = 0-2). The study of their optical behavior, reveals emission color variations from violet to yellow for the compounds containing the phosphines with one, two, and three phenylene spacers, respectively, and much more fine-tuning, from deep blue to brilliant blue for those intercalating alkynyl and phenylene spacers. Four of the new complexes were also characterized by X-ray diffraction crystallography, showing supramolecular structures formed through hydrogen bonding.