4,5-dioctylthiobenzene-1,2-dicarbonitrile | 214150-97-7

• 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-dioctylthiobenzene-1,2-dicarbonitrile
• 英文别名: 4,5-bis(octylthio)benzene-1,2-dinitrile；1,2-bis(octylthio)-4,5-dicyanobenzene；1,2-dicyano-4,5-bis(octylthio)benzene；4,5-bis(octylsulfanyl)phthalonitrile；1,2-Dicyano-4,5-dioctylthiobenzene；4,5-bis(octylthio)phthalodinitrile；4,5-Bis(octylsulfanyl)benzene-1,2-dicarbonitrile
• CAS: 214150-97-7
• 化学式: C₂₄H₃₆N₂S₂
• 分子量: 416.695
• InChiKey: DSZPHJYPCSFZCW-UHFFFAOYSA-N

物化性质

• 熔点：
  59.8 °C(Solv: ethanol (64-17-5))
• 沸点：
  539.0±50.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  28
• 可旋转键数：
  16
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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-dioctylthiobenzene-1,2-dicarbonitrile 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 三氯化硼 、 三乙胺 作用下， 以 对二甲苯 、 甲苯 为溶剂， 反应 24.5h， 生成 chloro[2-(1-pentynyl)-9,10,16,17-tetraoctylthio-7,12:14,19-diimino-21,5-nitrilo-5H-tribenzo[c,h,m][1,6,11]triazacyclopentadecinato(2-)-κN²²,κN²³,κN²⁴]-boron(III)
  参考文献：
  名称：

  调节亚酞菁-酞菁二聚体中的光诱导能量和电子转移事件。

  摘要：

  通过单炔基酞菁与不同的单碘亚酞菁之间的钯催化的交叉偶联反应，已经制备了一系列的亚酞菁-酞菁二价化合物。两个光敏单元之间的电子耦合通过刚性和π共轭的炔基间隔基来确保。另外，通过引入不同的外围取代基来调节亚酞菁部分的电子特性。循环和Osteryoung方波伏安法实验表明，从硫醚或无取代基变为硝基时，该亚基的还原电势可降低约400 mV。结果，可以微调电荷转移状态的能级，以便获得对每个子单元中光激发能的命运的控制。所采用的各种稳态和时间分辨光物理技术表明，当电荷转移态处于高能量状态时，就会发生从激发的亚酞菁到酞菁的定量单重态单重态能量转移机理。相反，通过降低电子供体和受体之间的氧化还原间隙来稳定自由基对，即使在极性低的溶剂（例如甲苯（Phi（ET）约为0.9））中，也可以实现高效的光诱导电子转移过程。这些特征以及这些分子集合体在整个UV / Vis光谱中显示的非凡吸收性截面，使其成为需要宽带光源

  DOI：

  10.1002/chem.200400779
• 作为产物：
  描述：

  1-辛硫醇 、 4,5-二氯邻苯二甲腈 在 potassium carbonate 作用下， 以 二甲基亚砜 为溶剂， 反应 12.0h， 生成 4,5-dioctylthiobenzene-1,2-dicarbonitrile
  参考文献：
  名称：

  连接原子和取代基位置对酞菁中甲亚胺氮碱度的主要影响

  摘要：

  在一系列取代基位置不同的酞菁 (Pcs) 上研究了偶氮甲碱氮的碱度，[公式：见正文]外围（[公式：见正文]-系列）和非外围取代的 Pcs（[公式：见正文]-系列），以及一种取代基（烷基硫烷基、烷氧基或烷基）。通过亲核取代或 Negishi 偶联制备合适的 3,6-或 4,5-二取代邻苯二甲腈。目标锌Pcs采用Linstead法合成。碱度采用吸收法研究1用三氟乙酸滴定后，氯仿中的 H NMR 光谱。平衡常数（log [公式：见正文]）表明系列内有显着差异。碱度降低如下： [分子式：见正文]-烷氧基 ≫ [分子式：见正文]-烷硫基 > [分子式：见正文]-烷氧基 > [分子式：见正文]-烷基 > [分子式：见正文]-烷硫基 ∼ [公式：见正文]-log [公式：见正文]高于 7 至 2.6 M [公式：见正文]的烷基。[分子式：见正文]-烷氧基和 [分子式：见正文]-烷基硫烷基 Pcs 的碱度

  DOI：

  10.1142/s1088424616500747

文献信息

• Trapping fullerenes with jellyfish-like subphthalocyanines
  作者：I. Sánchez-Molina、C. G. Claessens、B. Grimm、D. M. Guldi、T. Torres

  DOI：10.1039/c3sc21956a

  日期：——

  Six electronically different concave-shaped subphthalocyanines (SubPcs) have been prepared for testing the structural factors governing fullerenes encapsulation. Thus, the supramolecular interaction of SubPcs with C60 and C70 fullerenes in solution has been studied by Job's plot and titration experiments, which yielded quantitative information on both the stoichiometry and strength of the complexes in toluene solution. The importance of the electronic nature of the SubPc was demonstrated, as it influences not only the stability of the complex, but also its stoichiometry. Alkyl chains incorporated in hexaalkylthio-substituted SubPcs seem to in some way cooperate in the binding process and influence its kinetics. In the resulting 2 : 1 complexes, the large absorption cross section of SubPcs throughout the visible part of the spectrum is the beginning of an unidirectional energy transfer to funnel the excited state energy from the periphery (i.e., two SubPcs) to the core (i.e., C60 and C70).

  已经制备了六种电子性质不同的凹形次酞菁（SubPcs），用于测试决定富勒烯包封的结构因素。因此，通过Job图和滴定实验研究了SubPcs与C60和C70富勒烯在溶液中的超分子相互作用，这为甲苯溶液中复合物的化学计量和强度提供了定量信息。SubPc的电子性质的重要性得到了证明，因为它不仅影响复合物的稳定性，还影响其化学计量。六烷基硫取代的SubPcs中引入的烷基链似乎在某种程度上在结合过程中协同作用，并影响其动力学。在形成的2：1复合物中，SubPcs在整个可见光区域的较大吸收截面开始了从外围（即两个SubPcs）向核心（即C60和C70）的单向能量转移。
• 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。
• Halide effect in electron rich and deficient discotic phthalocyanines
  作者：Mohamed Ahmida、Raymond Larocque、M. Sharif Ahmed、Alina Vacaru、Bertrand Donnio、Daniel Guillon、S. Holger Eichhorn

  DOI：10.1039/b917169j

  日期：——

  A series of discotic octa- and tetra-alkylthio substituted phthalocyanines containing four Cl, Br, I atoms or twelve fluorine atoms have been prepared. All compounds display columnar mesomorphism as confirmed by polarized optical microscopy, thermal analysis, and variable temperature X-ray diffraction. Phthalocyanines containing halide atoms do not crystallize but form glassy or partially crystalline hexagonal columnar phases. Glass transition temperatures increase with increasing size of the halide atoms and with decreasing length of the alkyl chains. In contrast, all octa- and tetra-alkylthio substituted phthalocyanines crystallize and octa-substituted derivatives with aliphatic chain lengths of C5–7 exhibit tilted (rectangular) columnar mesophases. Cyclic and differential pulse voltammetry, UV-Vis spectroscopy, and quantum chemical calculations at the DFT level have been employed to determine frontier orbital energies of all synthesized and some reference phthalocyanines. Octa- and tetra-alkylthio substituted phthalocyanines are typical p-type semiconductors and the introduction of four Cl, Br, or I atoms lowers frontier orbital energies by only up to 0.1 eV and the optical gap by up to 0.03 eV. A significant decrease in LUMO energy by 0.5 eV to about −4 eV is observed for the fluorinated phthalocyanine, which is a value right at the border of organic n-type semiconductors that may be stable in air.

  合成了一系列盘形八烷基和四烷基硫取代的酞菁，包含四个氯、溴、碘原子或十二个氟原子。所有化合物均表现出柱状介晶性，已通过偏振光显微镜、热分析和变温X射线衍射确认。含卤素原子的酞菁不结晶，而是形成玻璃态或部分结晶的六角柱状相。玻璃转变温度随着卤素原子尺寸的增大和烷基链长度的缩短而升高。相对而言，所有八烷基和四烷基硫取代的酞菁均可结晶，且具有C5–7的烷基链长度的八取代衍生物显示出倾斜（矩形）柱状介晶相。利用循环伏安、差分脉冲伏安、紫外-可见光谱法及DFT水平的量子化学计算来确定所有合成的和一些参考酞菁的前沿轨道能量。八烷基和四烷基硫取代的酞菁是典型的p型半导体，引入四个氯、溴或碘原子仅使前沿轨道能量降低至多0.1 eV，光学带隙降低至多0.03 eV。氟化酞菁的LUMO能量显著降低0.5 eV，降至约−4 eV，这一数值恰好位于有机n型半导体的临界值，可能在空气中稳定。
• Phthalocyanine Synthesis in Ionic Liquids: Preparation of Differently Substituted Phthalocyanines in Tetrabutylammonium Bromide
  作者：Dennis K. Ng、Pui-Chi Lo、Diana Y. Cheng

  DOI：10.1055/s-2005-861855

  日期：——

  A series of alkylthio, alkoxy, and phenoxy phthalonitriles have been prepared by nucleophilic substitution reactions on suitable phthalonitrile precursors in molten tetrabutylammonium bromide. This readily available and inexpensive ionic liquid can also be used as a medium for the cyclization of these dinitriles giving the corresponding substituted phthalocyanines.

  通过在熔融四丁基溴化铵中对合适的邻苯二甲腈前体进行亲核取代反应，制备了一系列烷硫基、烷氧基和苯氧基邻苯二甲腈。这种容易获得且廉价的离子液体也可用作这些二腈环化产生相应取代的酞菁的介质。
• 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。