2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyanine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyanine
• 英文别名: 6,7,15,16,24,25,33,34-Octakis(hexylsulfanyl)-2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28,30(37),31,33,35-nonadecaene；6,7,15,16,24,25,33,34-octakis(hexylsulfanyl)-2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28,30(37),31,33,35-nonadecaene
• 化学式: C₈₀H₁₁₄N₈S₈
• 分子量: 1444.37
• InChiKey: QCCCMCWEKJOQOR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  29.1
• 重原子数：
  96
• 可旋转键数：
  48
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  311
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyanine 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以37%的产率得到2,3,9,10,16,17,23,24-octakis(hexylsulfonyl)phthalocyanine
  参考文献：
  名称：

  2,3,9,10,16,17,23,24-Octakis(hexylsulfonyl)phthalocyanines with good n-type semiconducting properties. Synthesis, spectroscopic, and electrochemical characteristics

  摘要：

  我们系统地研究了具有八个强夺电子己基磺酰基的外围八代酞菁化合物的合成。通过 4,5-二（己基磺酰基）邻苯二甲腈的直接环状四聚化或通过二亚氨基异吲哚啉中间体合成了三种新的酞菁 M[Pc(SO2C6H13)8] [Pc(SO2C6H13)8 = 2,3,9,10,16,17,23,24-octakis(hexylsulfonyl)phthalocyaninate; M = 2H (1), Cu (2), Zn (3)]。化合物 1-3 也可以通过间氯过苯甲酸氧化相应的 2,3,9,10,16,17,23,24-八(己硫基)酞菁化合物 M[Pc(SC6H13)8] （M = 2H、Cu、Zn）中的己硫基来制备。通过元素分析和一系列光谱方法对这些化合物进行了全面表征。通过循环伏安法（CV）和微分脉冲伏安法（DPV）研究了它们的电化学性质。通过密度函数理论（DFT）计算，研究了强夺电子基团对酞菁分子电子结构的影响。特别是 1-3 对饱和甘汞电极（SCE）的首次还原电位在-0.30∼-0.04 V 范围内，揭示了它们的 n 型半导体性质。其聚集体的电流-电压特性显示了良好的半导体特性，尤其是 1 和 2，其电导率值分别为 5.24 × 10-4 和 2.73 × 10-4 S m-1。

  DOI：

  10.1039/c1jm10295h
• 作为产物：
  描述：

  1,2-dicyano-4,5-bis(hexylthio)benzene 在 辛醇 、 lithium 、 溶剂黄146 作用下， 反应 72.0h， 生成 2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyanine
  参考文献：
  名称：

  Halide effect in electron rich and deficient discotic phthalocyanines

  摘要：

  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。

  DOI：

  10.1039/b917169j

文献信息

• Solution-processed single crystal microsheets of a novel dimeric phthalocyanine-involved triple-decker for high-performance ambipolar organic field effect transistors
  作者：Guang Lu、Xia Kong、Junshan Sun、Liangliang Zhang、Yanli Chen、Jianzhuang Jiang

  DOI：10.1039/c7cc06797f

  日期：——

  The well-defined single crystal microsheets of a novel dimeric phthalocyanine involved sandwich-type triple-decker complex [Pc(SC6H13)8]2Eu2[BiPc(SC6H13)12]Eu2[Pc(SC6H13)8]2 (1) are successfully prepared by a facile solution process. High-performance single crystal OFETs with the hole mobility of 18 cm2 V−1 s−1 and electron mobility of 0.3 cm2 V−1 s−1 are achieved.

  成功制备了一种新型的含三明治型三聚体复合物[Pc（SC6H13）8] 2Eu2 [BiPc（SC6H13）12] Eu2 [Pc（SC6H13）8] 2（1）的定义明确的单晶微片。通过轻松的解决方案过程。实现了具有18 cm2 V-1 s-1的空穴迁移率和0.3 cm2 V-1 s-1的电子迁移率的高性能单晶OFET。
• 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。
• Bis/tris[octakis(hexylthio)phthalocyaninato] europium(III) complexes: structure, spectroscopic, and electrochemical properties
  作者：Chunhua Huang、Yi Zhang、Junshan Sun、Yongzhong Bian、Dennis P. Arnold

  DOI：10.1142/s1088424612501465

  日期：2013.8

  Bis/tris(phthalocyaninato) europium double- and triple-decker complexes Eu [ Pc (β- SC 6 H 13)8]2 (1) and Eu 2[ Pc (β- SC 6 H 13)8]3 (2) [ Pc (β- SC 6 H 13)8 = 2, 3, 9, 10, 16, 17, 23, 24-octakis(hexylthio)phthalocyaninate] have been synthesized and characterized by a series of spectroscopic methods including mass, NMR, electronic absorption and IR spectroscopy in addition to elemental analysis. Their

  双/三（酞菁）铕双层和三层配合物 Eu [ Pc (β- SC6H13)8]2(1) 和欧盟2[ 个人计算机 (β- SC6H13)8]3(2) [ Pc (β-SC6H13)8= 2, 3, 9, 10, 16, 17, 23, 24-octakis(hexylthio)phthalocyaninate]已经合成并通过一系列光谱方法进行表征，包括质量、核磁共振、电子吸收和红外光谱以及元素分析。它们的分子结构已通过单晶 X 射线衍射分析和循环伏安法研究的电化学性质确定。
• Guerek, Ayse Guel; Bekaroglu, Oezer, Journal of the Chemical Society, Dalton Transactions, 1994, # 9, p. 1419 - 1424
  作者：Guerek, Ayse Guel、Bekaroglu, Oezer

  DOI：——

  日期：——
• 2,3,9,10,16,17,23,24-Octakis(hexylsulfonyl)phthalocyanines with good n-type semiconducting properties. Synthesis, spectroscopic, and electrochemical characteristics
  作者：Yi Zhang、Pan Ma、Peihua Zhu、Xianyao Zhang、Yingning Gao、Dongdong Qi、Yongzhong Bian、Nagao Kobayashi、Jianzhuang Jiang

  DOI：10.1039/c1jm10295h

  日期：——

  The synthesis of peripherally octa-substituted phthalocyanine compounds with eight strong electron-withdrawing hexylsulfonyl groups was systematically studied. Three new phthalocyanines M[Pc(SO2C6H13)8] [Pc(SO2C6H13)8 = 2,3,9,10,16,17,23,24-octakis(hexylsulfonyl)phthalocyaninate; M = 2H (1), Cu (2), Zn (3)] were synthesized via direct cyclic tetramerization of 4,5-di(hexylsulfonyl)phthalonitrile or through a diiminoisoindoline intermediate. Compounds 1–3 could alternatively be prepared by oxidation of the hexylthio substituents in corresponding 2,3,9,10,16,17,23,24-octakis(hexylthio)phthalocyanine compounds M[Pc(SC6H13)8] (M = 2H, Cu, Zn) with m-chloroperbenzoic acid. They were fully characterized by elemental analysis and a series of spectroscopic methods. Their electrochemistry was studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Density function theory (DFT) calculations were conducted to study the effect of the strong electron-withdrawing groups on the electronic structure of the phthalocyanine molecules. Particularly, the first reduction potentials in the range −0.30∼−0.04 V vs. the saturated calomel electrode (SCE) for 1–3 reveal their n-type semiconducting nature. The current–voltage characteristics of their aggregates demonstrate the good semiconducting properties especially for 1 and 2 with the conductivity value of 5.24 × 10−4 and 2.73 × 10−4 S m−1, respectively.

  我们系统地研究了具有八个强夺电子己基磺酰基的外围八代酞菁化合物的合成。通过 4,5-二（己基磺酰基）邻苯二甲腈的直接环状四聚化或通过二亚氨基异吲哚啉中间体合成了三种新的酞菁 M[Pc(SO2C6H13)8] [Pc(SO2C6H13)8 = 2,3,9,10,16,17,23,24-octakis(hexylsulfonyl)phthalocyaninate; M = 2H (1), Cu (2), Zn (3)]。化合物 1-3 也可以通过间氯过苯甲酸氧化相应的 2,3,9,10,16,17,23,24-八(己硫基)酞菁化合物 M[Pc(SC6H13)8] （M = 2H、Cu、Zn）中的己硫基来制备。通过元素分析和一系列光谱方法对这些化合物进行了全面表征。通过循环伏安法（CV）和微分脉冲伏安法（DPV）研究了它们的电化学性质。通过密度函数理论（DFT）计算，研究了强夺电子基团对酞菁分子电子结构的影响。特别是 1-3 对饱和甘汞电极（SCE）的首次还原电位在-0.30∼-0.04 V 范围内，揭示了它们的 n 型半导体性质。其聚集体的电流-电压特性显示了良好的半导体特性，尤其是 1 和 2，其电导率值分别为 5.24 × 10-4 和 2.73 × 10-4 S m-1。