2,2'-dicyanodiphenylacetylene | 57341-97-6

• 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: 2,2'-dicyanodiphenylacetylene
• 英文别名: 2-[2-(2-Cyanophenyl)ethynyl]benzonitrile；2-[2-(2-cyanophenyl)ethynyl]benzonitrile
• CAS: 57341-97-6
• 化学式: C₁₆H₈N₂
• 分子量: 228.253
• InChiKey: BGUNHFGCLTVZGI-UHFFFAOYSA-N

物化性质

• 沸点：
  464.2±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：

  silver trifluoromethanesulfonate 、 2,2'-dicyanodiphenylacetylene 以 xylene 为溶剂， 生成 [Ag(2,3'-DCPA)(CF₃SO₃)]
  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
• 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 2,2'-dicyanodiphenylacetylene
  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

• Conductance of <i>o</i>-carborane-based wires with different substitution patterns
  作者：Shi-Nuo Xu、Yan Zheng、Jing-Yao Ye、Zhong-Yang Chen、Jian-Feng Yan、Yan-Hou Geng、Wenjing Hong、Yao-Feng Yuan

  DOI：10.1039/d3dt00011g

  日期：——

  Interestingly, the three-dimensional structure in o-carborane-based wires can effectively promote the through-space transmission paths or the formation of stable molecular junctions compared to the corresponding phenyl-centered wires. Moreover, the significant conductance difference of o-carborane-based wires was due to the combination of multiple conduction channels and quantum interference. Understanding

  在这里，我们报告了具有多个传导通道的三种基于邻碳硼烷的分子线（邻-、间-和对-CN）的合成、结构和单分子电导。使用扫描隧道显微镜断裂结 (STM-BJ) 技术和理论计算研究了目标线与相应的以苯基为中心的线相比连通性的影响。有趣的是，与相应的以苯基为中心的导线相比，邻碳硼烷导线的三维结构可以有效促进空间传输路径或稳定分子连接的形成。此外， o的显着电导差异-基于碳硼烷的导线是由于多个传导通道和量子干涉的结合。了解不同桥接基团和锚定基团取代模式的影响为设计基于邻碳硼烷的多通道分子线提供了指导。
• 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.