4,5-bis(dodecylthio)phthalonitrile | 156903-57-0

• 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: 4,5-bis(dodecylthio)phthalonitrile
• 英文别名: 4,5-Bis(dodecylsulfanyl)benzene-1,2-dicarbonitrile
• CAS: 156903-57-0
• 化学式: C₃₂H₅₂N₂S₂
• 分子量: 528.91
• InChiKey: FIKKURPBMPRGOQ-UHFFFAOYSA-N

物化性质

• 沸点：
  625.6±55.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  13.5
• 重原子数：
  36
• 可旋转键数：
  24
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  98.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,5-bis(dodecylthio)phthalonitrile 在 zinc(II) acetate dihydrate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 戊醇 为溶剂， 反应 3.0h， 以73%的产率得到
  参考文献：
  名称：

  Phthalocyaninato complexes with peripheral alkylthio chains: Disk-like adsorbate species for the vertical anchoring of ligands onto gold surfaces

  摘要：

  Thin metalorganic films were prepared on gold by self-assembly of thioether-functionalised phthalocyaninato complexes from solution. The phthalocyaninato ligands used contain eight peripheral, beta-positioned, alkylthio substituents SR (1a: R = n-C8H17, 1b: R = n-C12H25), which serve as headgroups for surface binding and promote lateral assembly, while the disk-like phthalocyaninato core offers the scope for the attachment of axial ligands to the adsorbed molecules. This process was mimicked by coordination of pyridine (Py) to [Zn(1a)] and [Zn(1b)], respectively. The crystal structures of the products [Zn(1a)(Py)] and [Zn(1b)(Py)] were determined. The crystal structures of 4,5-bis(octylthio) phthalodinitrile and 4,5-bis(dodecylthio) phthalodinitrile were also determined. The films fabricated from [Mn(1a)Cl] and [Mn(1b)Cl] on gold were characterised by XPS, ToF-SIMS and NEXAFS spectroscopy, which revealed the presence of well-defined and homogeneous self-assembled monolayers (SAMs), whose constituents are bound to the substrate by thioether-gold linkages. The orientation of the macrocycles is predominantly parallel to the surface. Strong electronic interaction of the manganese(III) centre with the substrate leads to Cl loss upon adsorption and its reduction to Mn-II. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.02.048
• 作为产物：
  描述：

  4,5-二氯邻苯二甲腈 、 十二硫醇 在 potassium carbonate 作用下， 以 二甲基亚砜 为溶剂， 生成 4,5-bis(dodecylthio)phthalonitrile
  参考文献：
  名称：

  Novel columnar mesogen with octupolar optical nonlinearities: synthesis, mesogenic behavior and multiphoton-fluorescence-free hyperpolarizabilities of subphthalocyanines with long aliphatic chains†

  摘要：

  具有长硫烷基链的新型亚卟啉在室温下表现出六角柱状液晶相；其固有的第一超极化率值（β）通过超瑞利散射（HRS）在荧光抑制下测得为(189 ± 30) × 10⁻³⁰ esu，波长为1300 nm。

  DOI：

  10.1039/a904254g

文献信息

• Discotic liquid crystals of transition metal complexes 29: mesomorphism and charge transport properties of alkylthio-substituted phthalocyanine rare-earth metal sandwich complexes
  作者：Kazue Ban、Kaoru Nishizawa、Kazuchika Ohta、Anick M. van de Craats、John M. Warman、Iwao Yamamoto、Hirofusa Shirai

  DOI：10.1039/b003984p

  日期：——

  A series of bis[octakis(alkylthio)phthalocyaninato]rare-earth-metal(III) discotic compounds, [(CnS)8Pc]2M (M = Eu(III), Tb(III), Lu(III); n = 8, 10, 12, 14, 16, 18), has been synthesized. The mesomorphic and supramolecular structures have been investigated by using differential scanning calorimetry, polarization microscopy and temperature-dependent X-ray diffraction techniques. From the X-ray diffraction and spectroscopic results, it was revealed that in each of the rare-earth compound classes, [(CnS)8Pc]2Eu (n = 10, 12), [(CnS)8Pc]2Tb (n = 10, 12, 14) and [(CnS)8Pc]2Lu (n = 10, 12), derivatives were found which displayed a novel unique pseudo-hexagonal mesophase.The temperature dependence of the one-dimensional intracolumnar charge carrier mobilities, Σμ1D, has been measured for [(C12S)8Pc]2Lu and [(C18S)8Pc]2Lu using the PR-TRMC (pulse-radiolysis time-resolved microwave conductivity) technique. The mobility values in both the K and D phases are more than an order of magnitude larger than found previously for [(C12O)8Pc]2Lu and are close to the maximum values ever found for discotic materials. The lack of a decrease in Σμ1D at the mesophase to isotropic liquid transition suggests that these compounds may represent the first liquid phase organic semiconducting materials.

  一系列双[八烷基硫代邻苯二甲酰亚胺]稀土金属（III）盘状化合物[(CnS)8Pc]2M（M = Eu(III)、Tb(III)、Lu(III）；n = 8, 10, 12, 14, 16, 18）已被合成。通过差示扫描量热法、偏振显微镜和温度依赖的X射线衍射技术对各自的介晶态和超分子结构进行了研究。从X射线衍射和光谱结果显示，在每一类稀土化合物中，都发现了[(CnS)8Pc]2Eu（n = 10, 12）、[(CnS)8Pc]2Tb（n = 10, 12, 14）和[(CnS)8Pc]2Lu（n = 10, 12）衍生物，这些衍生物展现出了新颖的独特伪六角介相。通过脉冲辐解时分辨微波电导率（PR-TRMC）技术，测量了[(C12S)8Pc]2Lu和[(C18S)8Pc]2Lu的一维内列电荷载流子迁移率Σμ1D的温度依赖性。在K相和D相中的迁移率值均比以前在[(C12O)8Pc]2Lu中发现的高出一个数量级，并且接近于盘状材料所发现的最大值。在介相到各向同性液体过渡过程中Σμ1D没有降低，这表明这些化合物可能代表了首个液相有机半导体材料。
• Discotic liquid crystals of transition metal complexes 27: supramolecular structure of liquid crystalline octakisalkylthiophthalocyanines and their copper complexes
  作者：Kazue Ban、Kaoru Nishizawa、Kazuchika Ohta、Hirofusa Shirai

  DOI：10.1039/b000134l

  日期：——

  A series of octakisalkylthiophthalocyanines, (CnS)8PcH2 (n = 8, 10, 12, 16), and their copper(II) complexes, (CnS)8PcCu (n = 8, 10, 12, 16), have been synthesized. Their mesomorphism and supramolecular structures have been investigated by using differential scanning calorimetry, polarizing microscopy, temperature-dependent X-ray diffraction technique and temperature-dependent electronic spectroscopy. From the X-ray diffraction and electronic spectral results, it was revealed that each of the compounds has a Dh mesophase in which columnar structures the molecules form a mixture of the parts of aggregated dimers and monomers. The shapes of dimers are discussed by exciton coupling theory (Kasha's rule).

  合成了一系列八烷基硫代酞菁（CnS）8PcH2（n = 8, 10, 12, 16）及其铜(II)复合物（CnS）8PcCu（n = 8, 10, 12, 16）。通过差示扫描量热法、偏光显微镜、温度依赖的X射线衍射技术以及温度依赖的电子光谱对其相行为和超分子结构进行了研究。从X射线衍射和电子光谱结果显示，每种化合物都具有Dh相，其中柱状结构的分子形成了聚集的二聚体和单体部分的混合物。通过激子耦合理论（Kasha规则）讨论了二聚体的形状。
• Novel columnar mesogen with octupolar optical nonlinearities: synthesis, mesogenic behavior and multiphoton-fluorescence-free hyperpolarizabilities of subphthalocyanines with long aliphatic chains†
  作者：Seok Ho Kang、Kimoon Kim、Yoon-Sok Kang、Wang-Cheol Zin、Geert Olbrechts、Kurt Wostyn、Koen Clays、Andre Persoons

  DOI：10.1039/a904254g

  日期：——

  Novel subphthalocyanines with long thioalkyl chains exhibit hexagonal columnar mesophases at room temperature; their inherent first hyperpolarizability values (β) measured by hyper-Rayleigh scattering (HRS) with fluorescence suppression are (189 ± 30) × 10–30 esu at 1300 nm.

  具有长硫烷基链的新型亚卟啉在室温下表现出六角柱状液晶相；其固有的第一超极化率值（β）通过超瑞利散射（HRS）在荧光抑制下测得为(189 ± 30) × 10⁻³⁰ esu，波长为1300 nm。
• Dithienylcyclopentene-functionalised subphthalocyaninatoboron complexes: Photochromism, luminescence modulation and formation of self-assembled monolayers on gold
  作者：Tobias Weidner、Joe E. Baio、Johannes Seibel、Ulrich Siemeling

  DOI：10.1039/c1dt11644d

  日期：——

  Subphthalocyaninatoboron (SubPc) complexes bearing six peripheral n-dodecylthio substituents and an apical photochromic dithienylperfluorocyclopentene unit were prepared. The photoinduced isomerisation of the apical substituent from the open to the ring-closed form significantly influences the photoluminescence of the covalently attached SubPc unit, which is more efficiently quenched by the ring-closed form. Films on gold were fabricated from these multifunctional conjugates and characterised by near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS). The results are in accord with the formation of self-assembled monolayers based on dome-shaped SubPc-based anchor groups. Their chemisorption is primarily due to the peripheral n-dodecylthio substituents, giving rise to covalently attached thiolate as well as coordinatively bound thioether units, whose alkyl chains are in an almost parallel orientation to the surface.

  本研究制备了具有六个外围正十二烷硫基取代基和一个顶端光致变色二噻吩基全氟环戊二烯单元的亚酞菁亚硼（SubPc）复合物。顶端取代基在光诱导下从开环形式向闭环形式的异构化极大地影响了共价连接的 SubPc 单元的光致发光，而闭环形式能更有效地淬灭这种光致发光。利用这些多功能共轭物在金上制作了薄膜，并通过近边 X 射线吸收精细结构（NEXAFS）和 X 射线光电子能谱（XPS）对其进行了表征。结果与基于穹顶形 SubPc 基锚基团的自组装单层的形成相吻合。它们的化学吸附作用主要是由于外围的正十二烷硫基取代基，从而产生了共价连接的硫代硫酸盐以及配位结合的硫醚单元，其烷基链与表面的方向几乎平行。
• Noncentrosymmetric Columnar Liquid Crystals with the Bulk Photovoltaic Effect for Organic Photodetectors
  作者：Cheng Zhang、Kyohei Nakano、Masao Nakamura、Fumito Araoka、Keisuke Tajima、Daigo Miyajima

  DOI：10.1021/jacs.9b12710

  日期：2020.2.19

  into a noncentrosymmetric columnar liquid crystal with the help of a DC E-field. These columnar assemblies exhibit the BPVE over a wide range of wavelengths up to 650 nm. Furthermore, just by sandwiching this columnar assembly be-tween two ITO electrodes, the resultant device reaches a light-on/off ratio, ILight/IDark, as high as 6.6×103, indicating that the polar columnar assem-blies with SubPcs are

  体光伏效应（BPVE）由于其独特的特性而引起了广泛的关注，这是传统光伏效应无法实现的。然而，BPVE 在非中心对称材料中被观察到，并且主要针对无机材料进行了研究。在这里，我们报告了一种简单的亚酞菁 (SubPc) 衍生物，它在直流电场的帮助下组装成非中心对称柱状液晶。这些柱状组件在高达 650 nm 的宽波长范围内表现出 BPVE。此外，仅通过将这个柱状组件夹在两个 ITO 电极之间，所得到的器件就达到了高达 6.6×103 的开/关比 ILight/IDark，表明带有 SubPcs 的极性柱状组件很有前途用于光电探测器。