2-{2-[4-(4,7,10,13-tetraoxa-1-azacyclopentadecyl)phenyl]ethenyl}-3-(3-sulphopropyl)benzothiazolium betaine | 150196-53-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻唑类
• 英文名称: 2-{2-[4-(4,7,10,13-tetraoxa-1-azacyclopentadecyl)phenyl]ethenyl}-3-(3-sulphopropyl)benzothiazolium betaine
• CAS: 150196-53-5；150196-54-6
• 化学式: C₂₈H₃₆N₂O₇S₂
• 分子量: 576.735
• InChiKey: UDPKNMLPFPJNHZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.18
• 重原子数：
  39.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  101.24
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  2-{2-[4-(4,7,10,13-tetraoxa-1-azacyclopentadecyl)phenyl]ethenyl}-3-(3-sulphopropyl)benzothiazolium betaine 在 barium(II) perchlorate 作用下， 以 乙腈 为溶剂， 生成 C₂₈H₃₆BaN₂O₇S₂⁽²⁺⁾*2ClO₄^(1-)
  参考文献：
  名称：

  太阳能热存储的无贵金属分子机

  摘要：

  通过优化的合成程序制备了四种含苯并噻唑鎓冠醚的苯乙烯基染料。在苯并噻唑环的5位具有取代基的染料中的两种（4b和4d）是新合成的化合物。与已知的类似物相比，它们显示出更高的反式-顺式光异构化程度和更高能量形式的更长寿命。通过NMR，UV-vis，IR光谱和元素分析对系列中所有染料的化学结构进行了表征。阐明了染料的稳态光物理性质。测定了金属配合物的稳定性常数，并与参考染料的文献数据相吻合。反式的时间演变在实时方案中观察到顺式异构化。染料显示出其Ba 2+配合物的固有荧光低，E / Z光异构化的产率高，并且较高能级的寿命超过500秒。进行了B3LYP / 6-31 + G（d，p）级的密度泛函理论（DFT）计算，以预测系统的顺式和反式异构体的焓（H）和储能（ΔH）研究过。

  DOI：

  10.3762/bjoc.15.106
• 作为产物：
  描述：

  N,N-二羟乙基苯胺 在 哌啶 、 sodium hydride 、 三氯氧磷 作用下， 以 四氢呋喃 、 乙醇 、 乙酸乙酯 、 mineral oil 为溶剂， 反应 9.0h， 生成 2-{2-[4-(4,7,10,13-tetraoxa-1-azacyclopentadecyl)phenyl]ethenyl}-3-(3-sulphopropyl)benzothiazolium betaine
  参考文献：
  名称：

  不含稀土金属的E–Z光异构化对地面太阳辐照深红色部分的光子能量的累积

  摘要：

  以E - Z光可异构化有机材料的形式进行的大规模太阳能存储需要避免在所用过程的任何阶段使用稀土金属。在这里，据报道大大缩短了冠醚官能化的半菁染料的合成路线，与在未聚焦的阳光下相比，这种染料在极低的激发光强度下适用于有效的E - Z光异构化。较高的能量形式通过稀土游离阳离子（在这种情况下通过苯乙烯染料Ba 2+络合物）成功稳定。第一次E – Z光异构化被证明并直接观察到由激发光基本上红移相比的吸收光谱反式-到-顺式活性部分经由三线态-三线态湮灭上变频的过程。

  DOI：

  10.1039/d1tc01257f

文献信息

• Crown ether styryl dyes
  作者：S. P. Gromov、E. N. Ushakov、O. A. Fedorova、V. A. Soldatenkova、M. V. Alfimov

  DOI：10.1007/bf02496216

  日期：1997.6

  New crown ether-containing styryl dyes of the benzothiazole series containing an aza-15-crown-5-ether moiety were synthesized. Thetrans-cis-photoisomerization of these dyes and their analogs was studied; the effect of metal cations on the kinetics of darkcis-trans-isomerization was elucidated. The stability constants of the complexes of thecis-isomers of these dyes with Ca(ClO4)2 were estimated. The

  合成了含有 aza-15-crown-5-ether 部分的苯并噻唑系列新冠醚苯乙烯基染料。研究了这些染料及其类似物的反式-顺式-光异构化；阐明了金属阳离子对暗顺反式异构化动力学的影响。估计了这些染料的顺式异构体与 Ca(ClO4)2 的络合物的稳定性常数。在从阳离子染料传递到甜菜碱时，复合物稳定性的显着增加（超过三个数量级）归因于在 N 取代基的磺基和基团之间的顺式复合物中形成了分子内键。位于氮杂冠醚部分空腔中的金属阳离子。
• A Raman spectroscopic study of photochromic benzothiazolium dyes
  作者：I.K. Lednev、O.A. Fyedorova、S.P. Gromov、M.V. Alfimov、J.N. Moore、R.E. Hester

  DOI：10.1016/0584-8539(93)80065-i

  日期：1993.7

  Resonance Raman spectra using several excitation wavelengths have been obtained in the region 300-1750 cm-1 for two photochromic benzothiazolium dyes containing a crown ether ring. Bands arising from both cis- and trans-isomers have been distinguished by comparing the spectra observed at different resonances and under different sample conditions. Preliminary assignments of the bands have been made, allowing insight into the changes in structure and bonding which occur on photoisomerization.
• A Cation-Specific, Light-Controlled Transient Chromoionophore Based on a Benzothiazolium Styryl Azacrown Ether Dye
  作者：Igor K. Lednev、Ronald E. Hester、John N. Moore

  DOI：10.1021/ja964154j

  日期：1997.4.1

  A benzothiazolium styryl azacrown ether dye (1) and its complexation with Ba2+ and Na+ cations in acetonitrile solution have been studied by UV-vis absorption and emission spectroscopy, trans-1 is found to act as a normal chromoionophore for Ba2+ and Na+ at high concentration (greater than or equal to 10(-2) M) by complexation with the azacrown and as a light-controlled, transient chromoionophore specific for Ba2+ at low concentration (10(-5)-10(-3) M). A quantitative analysis of the complexation and thermal reactions following photolysis has enabled a detailed mechanism to be proposed: trans-1 photoisomerization produces cis-1, which is stabilized in the presence of Ba2+ by dual intramolecular complexation of the cation with both azacrown and sulfonate groups.
• Direct Observation of Photocontrolled Ion Release:  A Nanosecond Time-Resolved Spectroscopic Study of a Benzothiazolium Styryl Azacrown Ether Dye Complexed with Barium
  作者：Igor K. Lednev、Ronald E. Hester、John N. Moore

  DOI：10.1021/jp972360n

  日期：1997.10.1

  A benzothiazolium styryl azacrown ether dye (1) and its photocontrolled complexation with Ba2+ in acetonitrile solution have been studied by nanosecond time-resolved UV-visible absorption spectroscopy. Continuous visible irradiation of trans-1 in the presence of Ba2+ was used to generate a photostationary-state mixture with ''closed'' cis-1-Ba2+ present in high concentration: in this form, the barium cation is complexed with both the azacrown and a propylsulfonate group pendant to the benzothiazolium dye. A nanosecond UV photolysis pulse was used to induce photoisomerization of this ''closed'' cis-1-Ba2+ species. Time-resolved UV-visible absorption studies have revealed that the barium cation initially remains complexed to the azacrown in the trans-isomer formed <50 ns after UV photolysis and that the cation is subsequently released from the azacrown on a time scale of ca. 700 ns, consistent with the equilibrium composition of the solution expected from the thermal chemistry under these conditions. Along with time-resolved and steady-state studies of the effect of temperature and cation concentration, these studies have enabled a quantitative mechanism to be proposed for the thermal and photochemical ion-complexing properties of this dye. These direct observations demonstrate that sustained, photocontrolled ion release from an azacrown ether dye can be achieved within 1 mu s of photolysis.