1,2-bis(6-iodo-2-methyl-1-benzothiophen-3-yl)hexafluorocyclopentene | 167890-07-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻吩类
• 英文名称: 1,2-bis(6-iodo-2-methyl-1-benzothiophen-3-yl)hexafluorocyclopentene
• 英文别名: 3,3'-(Hexafluorocyclopentene-1,2-diyl)bis(2-methyl-6-iodobenzo[b]thiophene)；3-[3,3,4,4,5,5-hexafluoro-2-(6-iodo-2-methyl-1-benzothiophen-3-yl)cyclopenten-1-yl]-6-iodo-2-methyl-1-benzothiophene
• CAS: 167890-07-5
• 化学式: C₂₃H₁₂F₆I₂S₂
• 分子量: 720.28
• InChiKey: GVQVJSITSBTMHV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  33
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,2-bis(6-iodo-2-methyl-1-benzothiophen-3-yl)hexafluorocyclopentene 在 正丁基锂 、 potassium carbonate 、 sodium nitrite 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 19.08h， 生成 1-(2-methyl-1-benzothiophen-3-yl)-2-(6-(1-oxyl-4,4,5,5-tetramethylimidazolin-2-yl)-2-methyl-1-benzothiophen-3-yl)perfluorocyclopentene
  参考文献：
  名称：

  Effect of Imino Nitroxyl and Nitronyl Nitroxyl Groups on the Photochromic Reactivity of Diarylethenes

  摘要：

  Diarylethene derivatives having imino nitroxide and nitronyl nitroxide have been prepared to examine the effect of the radical substituents on the photochromic reactivity of 1,2-bis(2-methyl-1-benzothiophen-3-yl)perfluorocyclopentene. These radical substituents reduce the quantum yields of both cyclization and cycloreversion reactions. The nitronyl nitroxyl moiety is more effective to suppress the reactivity in comparison with the imino nitroxide moiety.

  DOI：

  10.1021/ol051463i
• 作为产物：
  描述：

  1,2-二[2-甲基苯并[B]噻吩-3-基]-3,3,4,4,5,5-六氟-1-环戊烯 在 硫酸 、 碘 、 溶剂黄146 、 高碘酸 作用下， 以 水 为溶剂， 生成 1,2-bis(6-iodo-2-methyl-1-benzothiophen-3-yl)hexafluorocyclopentene
  参考文献：
  名称：

  A perfluorocyclopentene based diarylethene bearing two terpyridine moieties – synthesis, photochemical properties and influence of transition metal ions

  摘要：

  报道了一种基于全氟环戊烯的二芳基乙烯醚，其中带有两个吡啶单元的合成。此外，还介绍了自由配体的光致变色性研究以及关于各种过渡金属离子对光致变色反应影响的调查。中央二芳基乙烯醚单元的光致变色性强烈依赖于存在的过渡金属，反之，光致变色反应似乎会影响双核Ru（II）配合物的MLCT跃迁。

  DOI：

  10.3762/bjoc.6.53

文献信息

• Photochromic glassy liquid crystals comprising mesogenic pendants to dithienylethene cores
  作者：Chunki Kim、Kenneth L. Marshall、Jason U. Wallace、Shaw H. Chen

  DOI：10.1039/b810955a

  日期：——

  Photochromic glassy liquid crystals were synthesized using dithienylethenes as the volume-excluding cores to which liquid crystalline mesogens were chemically bonded through alkyl spacers. Nematic, smectic, and cholesteric glassy liquid crystals were demonstrated with glass transition temperatures above 90 °C and clearing points up to 220 °C without traces of crystallization on cooling or crystalline melting on heating. A monodomain cholesteric glassy liquid crystalline film containing an enantiomeric 2-methylpropylene chiral spacer was characterized as a left-handed helical stack, exhibiting a selective reflection band centered at 686 nm, an orientational order parameter of 0.65 for the quasi-nematic layers, and a combination of reflective coloration with photoswitchable absorptive coloration.

  使用二噻吩乙烯作为体积排除核心，通过烷基间隔基化学键合液晶介晶，合成了光致变色玻璃态液晶。展示了玻璃化转变温度高于 90 °C、清亮点高达 220 °C 的向列相、层状相和胆甾相玻璃态液晶，在冷却过程中无结晶痕迹，在加热过程中无晶体熔化现象。含有手性 2-甲基丙烯基手性间隔基的单畴胆甾相玻璃态液晶薄膜，表现为左旋螺旋堆叠，具有中心位于 686 nm 的选择性反射带、准向列相层的取向序参数为 0.65，以及反射着色与光开关可吸收着色的组合。
• Reversible photocyclization of achiral dithienylperfluorocyclopentene dopants in a ferroelectric liquid crystal: bistable SSFLC photoswitching
  作者：Kenneth E. Maly、Peng Zhang、Michael D. Wand、Erwin Buncel、Robert P. Lemieux

  DOI：10.1039/b403188a

  日期：——

  The spontaneous polarization (PS) of a ferroelectric liquid crystal is modulated reversibly by photocyclization (λ = 313 nm) of dithienyl- and dibenzothienylperfluorocyclopentene dopants with relatively high aspect ratios. Photocyclization of these dopants causes a decrease of PS due to a photomechanical effect which may originate from a loss of conformational flexibility of the dopant upon photocyclization. The degree of PS photomodulation increases with dopant concentration up to the solubility limit of 3 mol%. The maximum polarization photomodulation, ΔPS = 16.2 nC cm−2, is achieved at 6 K below the Curie point with the dopant 1,2-bis(5-(4-heptyloxyphenyl)-2-methylthien-3-yl)perfluorocyclopentene (3c, 3 mol%). The resulting PS photoswitch is fatigue resistant and photochemically bistable. Polarized spectroscopy experiments suggest that the dopants form homogeneous solutions with the FLC host and are integrated within the layer structure of the SmC* phase, with their molecular long axes approximately coincident with the director. To the best of our knowledge, this is the first example of a bistable ferroelectric liquid crystal photoswitch to be reported in the literature.

  具有相对较高纵横比的二噻吩基和二苯并噻吩基全氟化环戊烯掺杂剂的光环化（λ = 313 nm）可逆地调节铁电液晶的自发极化（PS）。由于光机械效应，这些掺杂剂的光环化会导致 PS 值下降，这种效应可能源于掺杂剂在光环化时构象灵活性的丧失。PS 光调节的程度随着掺杂剂浓度的增加而增加，最高可达 3 摩尔%的溶解极限。当掺杂剂为 1,2-双(5-(4-庚氧基苯基)-2-甲基噻吩-3-基)全氟环戊烯（3c，3 摩尔%）时，在低于居里点 6 K 的温度下可实现最大偏振光调制，即 ΔPS = 16.2 nC cm-2。由此产生的 PS 光开关具有抗疲劳性和光化学双稳态性。偏振光谱实验表明，掺杂剂与 FLC 主成分形成均相溶液，并与 SmC* 相的层结构融为一体，其分子长轴与方向大致重合。据我们所知，这是文献中报道的第一个双稳态铁电液晶光开关实例。
• Diastereoselective self-assembly of a triple-stranded europium helicate with light modulated chiroptical properties
  作者：Zhihui Zhang、Yanyan Zhou、Ting Gao、Pengfei Yan、Xiaoyan Zou、Hongfeng Li

  DOI：10.1039/d1dt00251a

  日期：——

  The Eu³⁺ helicate that combines supramolecular chirality, luminescence and photochromic properties shows light-responsive chiroptical (ECD and CPL) switching properties upon alternating UV and visible light irradiation.

  这段话的中文翻译如下：

  由Eu³⁺离子组成的超分子手性螺环化合物，具有发光和光致变色性能，展现出光响应性的手性光学（ECD和CPL）开关特性，通过交替的紫外线和可见光辐照实现。

• Molecular Design Strategy toward Diarylethenes That Photoswitch with Visible Light
  作者：Tuyoshi Fukaminato、Takashi Hirose、Takao Doi、Masaki Hazama、Kenji Matsuda、Masahiro Irie

  DOI：10.1021/ja5090749

  日期：2014.12.10

  derivative (3) undergoes a photocyclization reaction upon irradiation with 560 nm light and the closed-isomer converts to the open-ring isomer upon irradiation with 405 nm light. The high photoconversion yields (>90%) were achieved for both photocyclization and photocycloreversion reactions. The photoreactivity induced by visible light irradiation and the molecular design strategy were discussed based on theoretical

  在可见光照射下可逆切换的光敏分子是生物和成像应用中最具吸引力的目标之一。制备此类光开关的一种可能方法是延长分子的 π 共轭长度并将吸收带移至更长的波长。尽管基于这种方法对二芳基乙烯 (DAE) 光开关进行了多次尝试，但当通过在 DAE 单元中芳基的侧位连接芳香族染料来延长共轭长度时，DAE 衍生物的光反应性被显着抑制。在本研究中，我们通过在DAE单元的活性碳原子处引入芳香染料，优化各组分的轨道能级，成功制备了可见光活性DAE衍生物，控制芳香染料和DAE单元的相互取向。DAE 衍生物 (3) 在 560 nm 光照射下发生光环化反应，闭环异构体在 405 nm 光照射下转化为开环异构体。光环化和光环回复反应均实现了高光转化产率 (>90%)。基于理论计算讨论了可见光照射引起的光反应性和分子设计策略。
• Photoswitching of the Magnetic Interaction between a Copper(II) Ion and a Nitroxide Radical by Using a Photochromic Spin Coupler
  作者：Kohsuke Takayama、Kenji Matsuda、Masahiro Irie

  DOI：10.1002/chem.200305154

  日期：2003.11.21

  Photoswitching of an intramolecular spin exchange interaction between a copper(II) ion and a nitroxyl radical by using a metal complex of diarylethene has been studied by means of ESR spectroscopy. As a coordination ligand, a diarylethene with a 1,10-phenanthroline ring and nitronyl nitroxide radical was synthesized. Mixing the diarylethene ligand with [Cu(hfac)(2)] (hfac=hexafluoroacetylacetone) in

  通过ESR光谱研究了通过使用二芳基乙烯的金属络合物对铜（II）离子与硝基氧基之间的分子内自旋交换相互作用的光开关。作为配位体，合成了具有1,10-菲咯啉环和硝酰基硝基氧自由基的二芳基乙烯。将二芳基乙烯配体与[Cu（hfac）（2）]（hfac =六氟乙酰丙酮）在甲苯中混合会导致由于络合而导致闭环异构体的最大吸收峰发生色变。Cu（II）配合物的开环异构体在室温下在甲苯中进行ESR测量，得出的光谱是氮氧自由基和Cu（II）光谱的叠加。当样品以366 nm的光照射时，由于硝氧基自由基和Cu（II）之间的交换作用较大，出现了一个新的峰。此ESR测量表明，自旋交换相互作用的强度通过光辐照改变了160倍以上。这是二芳基乙烯系统中记录的最大磁性光开关现象。