2-[(3-cyanophenyl)ethynyl]benzonitrile | 196080-59-8

• 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-[(3-cyanophenyl)ethynyl]benzonitrile
• 英文别名: 2,3'-dicyanodiphenylacetylene；2-[2-(3-Cyanophenyl)ethynyl]benzonitrile；2-[2-(3-cyanophenyl)ethynyl]benzonitrile
• CAS: 196080-59-8
• 化学式: C₁₆H₈N₂
• 分子量: 228.253
• InChiKey: YZCSDTPVBVBWQP-UHFFFAOYSA-N

物化性质

• 熔点：
  117-118 °C(Solv: hexane (110-54-3); benzene (71-43-2))
• 沸点：
  444.2±30.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[(3-cyanophenyl)ethynyl]benzonitrile 在 哌啶 、 lithium aluminium tetrahydride 作用下， 以 乙醚 、 乙酸酐 为溶剂， 反应 21.75h， 生成
  参考文献：
  名称：

  双（花青素）均相折叠二聚体：定义明确的染料聚集体几何形状中电子和光谱变化的评估。

  摘要：

  合成了三种不同共轭长度的生色团的三双（花青）染料，并通过紫外/可见吸收光谱研究了分子内的聚集过程。在溶剂极性变化时观察到的光谱变化揭示了折叠过程，导致两个生色团的表面π堆叠，随着生色团长度和溶剂极性的增加，聚集趋势降低。单体参考染料的溶剂依赖性UV / Vis研究表明，在非极性溶剂中具有较长聚次甲基链的染料的多烯样特性显着增加，由于染料堆栈内相邻发色团的极化作用，聚集后这种现象会逆转。

  DOI：

  10.1002/chem.201901754
• 作为产物：
  描述：

  2-[2-(三甲基硅烷基)乙炔基]-苯甲腈 在 copper(l) iodide 、 potassium carbonate 、 三乙胺 、 三苯基膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 21.0h， 生成 2-[(3-cyanophenyl)ethynyl]benzonitrile
  参考文献：
  名称：

  Association of Dicyanodiphenylacetylenes with Silver(I) Salts in Solution and Solid State:  Electrospray Ionization Mass Spectrometry Samples Aggregates at Subsaturated Concentrations

  摘要：

  Complexes of 2,3'-dicyanodiphenylacetylene (2,3'-DCPA, 1), 2,2'-dicyanodiphenylacetylene (2,2'-DCPA, 2), and 2,4'-dicyanodiphenylacetylene (2,4'-DCPA, 3) with silver(I) salts have been characterized in the solid state by single-crystal X-ray analysis. In addition, aggregates of compounds 1-3 and silver(I) ions have been identified in solution by electrospray ionization mass spectrometry (ESI-MS). The topology of the structures in the solid state, namely finite versus infinite, is found to depend on the substitution pattern of nitrile groups on diphenylacetylene. For 2,3'-DCPA. (1), crystallization with silver(I) triflate (AgCF3SO3), silver(I) perchlorate hydrate (AgClO4 . xH(2)O, x similar to 1), or silver(I) hexafluoroantimonate (AgSbF6) produces cyclic dimers of composition [Ag(1)(X)](2) (X = CF3SO3-(4) or ClO4- (5)) and {[Ag(1)](SbF6)}(2) (6). For these structures, 2,3'-DCPA coordinates to silver(I) ions in a cisoid conformation with respect to the orientation of nitrile groups. Significant deformations of the cyclic dimers are observed as a function of the counterion employed. In contrast to the finite structures involving 2,3'-DCPA, crystallization of 2,2'-DCPA (2) with AgCF3SO3 yields the infinite chain structure [Ag(2)(CF3SO3)] (7). 2,2'-DCPA coordinates to silver(I) in a transoid conformation resulting in a ''half-bow-tie'' motif for the chains. Crystallization of 2,4'-DCPA (3) with AgCF3SO3 produces the infinite, undulating sheet structure [Ag(3)(CF3SO3)] (8) in which helical chains of 2,4'-DCPA coordinated to silver(I) ions are bridged by triflate counterions. Positive ion ESI-MS of solutions of 2,3'-DCPA (1) and AgCF3SO3, AgClO4 . H2O, or AgSbF6 in acetone or acetonitrile show a distribution of aggregates including [Ag-2(1)(2)(X)](+) (X = CF3SO3-, ClO4-, or SbF6-). The composition of these species corresponds to that of the cyclic dimers of complexes 4-6 minus one counterion, X. With 2,2'-DCPA (2) and AgCF3SO3 in acetone or acetonitrile, the aggregates [Ag(2)](+) and [Ag(2)(2)](+) are observed and higher adducts are noted to be present in much lower abundance. It is believed that the predominance of adducts involving one silver(I) ion is due to the formation of chelated species in solution in which 2,2'-DCPA coordinates to a silver(I) ion in a cisoid conformation. Molecular modeling suggests that such species are viable. ESI-MS of 2,4'-DCPA (3) and AgCF3SO3 in acetone or acetonitrile shows the existence of [Ag(3)](+) as well as higher aggregates which are less prevalent. For a given Ligand, aggregation at concentrations of the Ligand and silver(I) salt of ca. 10(-3) M is significant in acetone, however, it is largely disrupted in acetonitrile due to the predominance of acetonitrile Ag(I) adducts. Analysis of the ESI-MS data for all three ligands with AgCF3SO3 in acetone or acetonitrile shows that the aggregate [Ag-2(L)(2)(CF3SO3)](+) is most abundant for L = 2,3'-DCPA (1). It is postulated that the relatively high abundance of [Ag-2(1)(2)(CF3SO3)](+) is indicative of the formation of a cyclic dimer in solution that resembles complex 4.Similarly, it is believed that cyclic dimers exist in solution with ClO4- and SbF6- as well.

  DOI：

  10.1021/ja971135g

文献信息

• Block modification of rod-shaped π conjugated carbon frameworks with donor and acceptor groups toward highly fluorescent molecules: synthesis and emission characteristics
  作者：Takanori Ochi、Yoshihiro Yamaguchi、Tateaki Wakamiya、Yoshio Matsubara、Zen-ichi Yoshida

  DOI：10.1039/b717832h

  日期：——

  To create organic molecules that are highly fluorescent at a longer wavelength region, we investigated the synthesis (using Pd-catalyzed cross-coupling) and photophysical properties (Φf, λem, τ, λabs, and ε) of the following π conjugated molecular rods consisting of p-phenyleneethynylene units modified by donor (OMe) and/or acceptor (CN) groups: (1) side-donor modification systems (SD systems), (2) side-acceptor modification systems (SA systems), and (3) systems consisting of a donor block and an acceptor block (BL systems). As a consequence, very high Φf values (>0.95) were obtained for BL systems. Bathochromic shifts of λem for the same π conjugation length were largest for BL systems. Thus we succeeded in creating highly efficient light emitters at a longer wavelength region by block modification (e.g., Φf = 0.97, λem = 464 nm for BL-9). Considerably intense solid emission (Φf ∼ 0.5) at a longer wavelength region (500–560 nm) was also found for BL systems. It has been found that BL-6 and BL-8 exhibit interesting two photon absorption characteristics.

  为了创造在较长波长区域高度荧光的有机分子，我们研究了以下由供体（OMe）和/或受体（CN）修饰的对亚苯基乙炔单元组成的π共轭分子杆的合成（使用钯催化交叉耦合）和光物理性质（Φf，λem，τ，λabs，和ε）：（1）侧供体修饰系统（SD系统），（2）侧受体修饰系统（SA系统），以及（3）由供体块和受体块组成的系统（BL系统）。因此，我们得到了非常高的Φf值（>0.95）用于BL系统。对于相同的π共轭长度，BL系统的λem的向红移位最大。因此，通过块修饰（例如，对于BL-9，Φf = 0.97，λem = 464 nm），我们成功地创造出了在较长波长区域高效发光体。我们还发现在较长波长区域（500–560 nm），BL系统表现出相当强烈的固态发射（Φf ≈ 0.5）。研究发现，BL-6和BL-8具有有趣的双光子吸收特性。
• Association of Dicyanodiphenylacetylenes with Silver(I) Salts in Solution and Solid State:  Electrospray Ionization Mass Spectrometry Samples Aggregates at Subsaturated Concentrations
  作者：Keith A. Hirsch、Scott R. Wilson、Jeffrey S. Moore

  DOI：10.1021/ja971135g

  日期：1997.10.1

  Complexes of 2,3'-dicyanodiphenylacetylene (2,3'-DCPA, 1), 2,2'-dicyanodiphenylacetylene (2,2'-DCPA, 2), and 2,4'-dicyanodiphenylacetylene (2,4'-DCPA, 3) with silver(I) salts have been characterized in the solid state by single-crystal X-ray analysis. In addition, aggregates of compounds 1-3 and silver(I) ions have been identified in solution by electrospray ionization mass spectrometry (ESI-MS). The topology of the structures in the solid state, namely finite versus infinite, is found to depend on the substitution pattern of nitrile groups on diphenylacetylene. For 2,3'-DCPA. (1), crystallization with silver(I) triflate (AgCF3SO3), silver(I) perchlorate hydrate (AgClO4 . xH(2)O, x similar to 1), or silver(I) hexafluoroantimonate (AgSbF6) produces cyclic dimers of composition [Ag(1)(X)](2) (X = CF3SO3-(4) or ClO4- (5)) and [Ag(1)](SbF6)}(2) (6). For these structures, 2,3'-DCPA coordinates to silver(I) ions in a cisoid conformation with respect to the orientation of nitrile groups. Significant deformations of the cyclic dimers are observed as a function of the counterion employed. In contrast to the finite structures involving 2,3'-DCPA, crystallization of 2,2'-DCPA (2) with AgCF3SO3 yields the infinite chain structure [Ag(2)(CF3SO3)] (7). 2,2'-DCPA coordinates to silver(I) in a transoid conformation resulting in a ''half-bow-tie'' motif for the chains. Crystallization of 2,4'-DCPA (3) with AgCF3SO3 produces the infinite, undulating sheet structure [Ag(3)(CF3SO3)] (8) in which helical chains of 2,4'-DCPA coordinated to silver(I) ions are bridged by triflate counterions. Positive ion ESI-MS of solutions of 2,3'-DCPA (1) and AgCF3SO3, AgClO4 . H2O, or AgSbF6 in acetone or acetonitrile show a distribution of aggregates including [Ag-2(1)(2)(X)](+) (X = CF3SO3-, ClO4-, or SbF6-). The composition of these species corresponds to that of the cyclic dimers of complexes 4-6 minus one counterion, X. With 2,2'-DCPA (2) and AgCF3SO3 in acetone or acetonitrile, the aggregates [Ag(2)](+) and [Ag(2)(2)](+) are observed and higher adducts are noted to be present in much lower abundance. It is believed that the predominance of adducts involving one silver(I) ion is due to the formation of chelated species in solution in which 2,2'-DCPA coordinates to a silver(I) ion in a cisoid conformation. Molecular modeling suggests that such species are viable. ESI-MS of 2,4'-DCPA (3) and AgCF3SO3 in acetone or acetonitrile shows the existence of [Ag(3)](+) as well as higher aggregates which are less prevalent. For a given Ligand, aggregation at concentrations of the Ligand and silver(I) salt of ca. 10(-3) M is significant in acetone, however, it is largely disrupted in acetonitrile due to the predominance of acetonitrile Ag(I) adducts. Analysis of the ESI-MS data for all three ligands with AgCF3SO3 in acetone or acetonitrile shows that the aggregate [Ag-2(L)(2)(CF3SO3)](+) is most abundant for L = 2,3'-DCPA (1). It is postulated that the relatively high abundance of [Ag-2(1)(2)(CF3SO3)](+) is indicative of the formation of a cyclic dimer in solution that resembles complex 4.Similarly, it is believed that cyclic dimers exist in solution with ClO4- and SbF6- as well.
• Bis(merocyanine) Homo‐Folda‐Dimers: Evaluation of Electronic and Spectral Changes in Well‐Defined Dye Aggregate Geometries
  作者：Eva Kirchner、David Bialas、Marius Wehner、David Schmidt、Frank Würthner

  DOI：10.1002/chem.201901754

  日期：——

  comprising chromophores of different conjugation lengths has been synthesized and the intramolecular aggregation process was investigated by UV/Vis absorption spectroscopy. The spectral changes observed upon variation of the solvent polarity reveal a folding process resulting in a cofacial π-stack of two chromophores with a decrease of the aggregation tendency with increasing chromophore length and solvent

  合成了三种不同共轭长度的生色团的三双（花青）染料，并通过紫外/可见吸收光谱研究了分子内的聚集过程。在溶剂极性变化时观察到的光谱变化揭示了折叠过程，导致两个生色团的表面π堆叠，随着生色团长度和溶剂极性的增加，聚集趋势降低。单体参考染料的溶剂依赖性UV / Vis研究表明，在非极性溶剂中具有较长聚次甲基链的染料的多烯样特性显着增加，由于染料堆栈内相邻发色团的极化作用，聚集后这种现象会逆转。