4,5-bis(hexadecylthio)benzene-1,2-dinitrile | 298694-11-8

• 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: 4,5-bis(hexadecylthio)benzene-1,2-dinitrile
• 英文别名: 4,5-di(n-hexadecylthio)phthalonitrile；4,5-bis(hexadecylthio)phthalonitrile；di(hexadecylthio)-4,5-dicyanobenzene；4,5-Bis(hexadecylsulfanyl)benzene-1,2-dicarbonitrile；4,5-bis(hexadecylsulfanyl)benzene-1,2-dicarbonitrile
• CAS: 298694-11-8
• 化学式: C₄₀H₆₈N₂S₂
• 分子量: 641.125
• InChiKey: VGBYXDMUMKCCNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.9
• 重原子数：
  44
• 可旋转键数：
  32
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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(hexadecylthio)benzene-1,2-dinitrile 在 lead(II) oxide 作用下， 反应 5.0h， 以19%的产率得到2,3,9,10,16,17,23,24-octakis(n-hexadecylthio)phthalocyaninato lead(II)
  参考文献：
  名称：

  Liquid crystalline octasubstituted lead(ii) phthalocyanines: effects of alkoxy and alkylthio substituents on film alignment and electrical properties

  摘要：

  利用 1H 和 13C NMR、UV-Vis、IR 和质谱以及元素分析法合成了外围位置含有烷硫基和烷氧基的八代酞菁铅（II），并对其进行了表征。通过差示扫描量热法、偏振光学显微镜和 X 射线衍射法研究了八取代酞菁铅（II）的介电性质。为了研究这些分子薄膜的 J（V）特性，制备了夹层结构 ITO/PbPc/In。薄膜在热处理前后的不同行为预计会导致薄膜中分子柱状堆叠内部的排列发生变化。

  DOI：

  10.1039/c2nj40247e
• 作为产物：
  描述：

  1-十六烷硫醇 、 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 1.5h， 以74.2%的产率得到4,5-bis(hexadecylthio)benzene-1,2-dinitrile
  参考文献：
  名称：

  Discotic liquid crystals of transition metal complexes 50: spiranthes-like supramolecular structure of phthalocyanine-fullerene dyads

  摘要：

  我们采用开发的合成方法合成了新型液晶 Pc - C 60 二元化合物 (CnS)6PcCu-C60 (n = 14, 16, 18: 1a-1c)，以研究其介形性和配位行为。n = 14、16、18 时，(CnS)6PcCu-C60 的每个二元体在两块玻璃板之间的 Colho 介相中都显示出完美的同向配位，n = 14 时在一块玻璃板上也显示出完美的同向配位，但母体 Pc 化合物 (CnS)8PcCu 和 Pc 前体 (CnS)6PcCu-OH 和 (CnS)6PcCu-OFBA 均未显示出同向配位。这可能是由于富勒烯与玻璃表面之间具有很强的亲和力。虽然目前还不清楚其中的原因，但这对分子设计制备各向同性配位的盘状液晶是非常有用的指导。非常有趣的是，球形的 C 60 部分在圆盘状的 Pc 部分形成的柱子周围形成螺旋结构，这种超分子结构非常像螺旋藻。这种类似螺旋藻的超分子结构与一维纳米阵列兼容，有望实现太阳能电池的高转换效率。

  DOI：

  10.1142/s1088424614500072

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。
• 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。
• Self-Organization of Phthalocyanine−[60]Fullerene Dyads in Liquid Crystals
  作者：Andrés de la Escosura、M. Victoria Martínez-Díaz、Joaquín Barberá、Tomás Torres

  DOI：10.1021/jo7022763

  日期：2008.2.1

  The use of blends in which a mesogen induces mesomorphism into a non-mesogenic compound has made possible the self-organization of phthalocyanine−[60]fullerene (Pc-C60) dyads into liquid crystals. Pc-C60 dyads 1, 2, or 3, in which two photoactive units are brought together by a phenylenevinylene spacer, have been synthesized through a Heck reaction that links 4-vinylbenzaldehyde to a monoiodophthalocyanine

  使用其中液晶元将介晶性诱导为非介晶化合物的共混物，使得酞菁-[60]富勒烯（Pc-C 60）二元化合物自组织成液晶成为可能。PC-C 60个成对层1，2，或3，其中两个光活性单元由亚苯基亚乙烯基间隔件放在一起时，已通过Heck反应合成的链接4-乙烯基苯甲醛到monoiodophthalocyanine前体，然后通过甲亚胺叶立德的标准环加成产生从甲酰基Pc衍生物和N-甲基甘氨酸到C 60的双键之一。通过形成不同的混合物的介晶性质和热性质的液晶性酞菁4和成对层1，2，或3使用偏光显微镜（POM），差示扫描量热法（DSC），和X射线衍射（XRD）进行了研究。共混物的DSC图显示从晶态到中间相的清晰过渡，并且从粉末衍射实验获得的测量结构参数与盘状六方柱状（Col h）结构一致。考虑到在Pc-C 60 dyad和酞菁4的分离分子域中的偏析由于柱直径的不匹配和纯二元体缺乏介晶特性而将导致同构现象的发生