cyclobis(paraquat-p-phenylene) | 117271-76-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: cyclobis(paraquat-p-phenylene)
• 英文别名: blue box；5,12,19,26-tetrazoniaheptacyclo[24.2.2.22,5.27,10.212,15.216,19.221,24]tetraconta-1(29),2(40),3,5(39),7,9,12,14,16(34),17,19(33),21(32),22,24(31),26(30),27,35,37-octadecaene
• CAS: 117271-76-8
• 化学式: C₃₆H₃₂N₄
• 分子量: 520.677
• InChiKey: URORLZXVTFVIPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  40
• 可旋转键数：
  0
• 环数：
  16.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  15.5
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  四硫富瓦烯 、 cyclobis(paraquat-p-phenylene) 以 乙腈 为溶剂， 生成 TTF*CBPQT(4+)
  参考文献：
  名称：

  Turning on Resonant SERRS Using the Chromophore−Plasmon Coupling Created by Host−Guest Complexation at a Plasmonic Nanoarray

  摘要：

  An active molecular plasmonics system is demonstrated where a supramolecular chromophore generated in a host guest binding event couples with the localized surface plasmon resonance (LSPR) arising from gold nanodisc gratings. This coupling was achieved by wavelength-matching the chromophore and the LSPR with the laser excitation, thus giving rise to surface-enhanced resonance Raman scattering (SERRS). The chromophore is a broad charge-transfer (CT) band centered at 865 nm (epsilon = 3500 M-1 cm(-1)) generated by the complexation of cyclobis(paraquat-p-phenylene) (CBPQT(4+)) and the guest molecule tetrathiafulvalene (TTF). The substrates consist of sub-1-mu m gold nanodisc arrays which display dimension-tunable plasmon wavelengths (600-1000 nm). The vibrational spectra of the complex arising from SERRS (lambda(exc) = 785 nm) were generated by irradiating an array (lambda(LSPR) = 765 nm) through the solution to give a chromophore-specific signature with the intensities surface enhanced by similar to 10(5). Surface adsorption of the empty and complexed CBPQT(4+) is also implicated in bringing the chromophore into the electric field arising from the surface-localized plasmon. In a titration experiment, the SERRS effect was then used to verify the role of resonance in turning on the spectrum and to accurately quantify the binding between surface-adsorbed CBPQT(4+) and TTF. The use of a nonpatterned gold substrate as well as a color mismatched complex did not show the enhancement, thus validating that spectral overlap between the chromophore and plasmon resonance is key for resonance surface enhancement. Simulations of the electric fields of the arrays are consistent with interdisc plasmon coupling and the observed enhancement factors. The creation of a responsive plasmonic device upon the addition of the guest molecule and the subsequent coupling of the CT chromophore to the plasmon presents favorable opportunities for applications in molecular sensing and active molecular plasmonics.

  DOI：

  10.1021/ja910155b
• 作为产物：
  描述：

  在 tris(p-bromophenylammoniumyl) hexachloroantimonate 作用下， 生成 cyclobis(paraquat-p-phenylene)
  参考文献：
  名称：

  A Radically Configurable Six-State Compound

  摘要：

  锰等金属在氧化状态范围较宽的情况下相对稳定。相比之下，纯有机化合物很少能够在没有伴随着断裂或耦合反应的情况下逐步添加或去除电子。

  Barnes 等人（第429页；见Benniston的观点）报道了一种猫环化合物（由相互交错的环组成的化合物），其中拓扑结构稳定了六种不同的状态，这些状态逐步不同，其框架中存在或不存在一个或两个电子。七氧化态对氧气暴露表现出了非常强的韧性。

  DOI：

  10.1126/science.1228429

文献信息

• Encapsulation and Stabilization of a Donor–Acceptor Stenhouse Adduct Isomer in Water Inside the Blue Box: A Combined Experimental and Theoretical Approach
  作者：Sujay Mukhopadhyay、Arnab Sarkar、Sourav Ghoshal、Pranab Sarkar、Koushik Dhara、Pabitra Chattopadhyay

  DOI：10.1021/acs.jpcb.1c03890

  日期：2021.7.8

  adducts (DASAs), a new type of photochromic molecules showing dual color in two different isomeric forms in solution phase, using Meldrum acid (DASA-Mel) and barbituric acid (DASA-Bar), along with a naphthalimide derivative to obtain interesting fluorescence properties. DASA-Mel was found to have fast photochromic conversion in comparison to DASA-Bar, evident from ultraviolet–visible (UV–vis) and fluorescence

  我们使用 Meldrum 酸 (DASA-Mel) 和巴比妥酸 (DASA-Bar) 合成了两种类型的供体 - 受体 Stenhouse 加合物 (DASA)，这是一种新型光致变色分子，在溶液相中以两种不同的异构形式显示双色。与萘酰亚胺衍生物获得有趣的荧光特性。与 DASA-Bar 相比，发现 DASA-Mel 具有快速的光致变色转换，这从紫外-可见光 (UV-vis) 和荧光光谱研究中可见一斑。DASA-Mel 的有色形式被封装在水溶性 Stoddart 蓝盒内，并且比 DASA-Bar 更快地溶于水。有趣的是，竞争性封装实验表明 DASA-Mel 被选择性地封装在水中的蓝色盒子内，而 DASA-Bar 大部分在离心后从溶液中分离出来，1 H 和 DOSY NMR 和质谱。此外，我们通过密度泛函理论 (DFT) 优化发现，与 DASA-Bar 相比，DASA-Mel 的开放形式在水介质中的封装反应过程中更稳定。封装的
• Cooperative Self‐Assembly of a Quaternary Complex Formed by Two Cucurbit[7]uril Hosts, Cyclobis(paraquat‐ <i>p</i> ‐phenylene), and a “Designer” Guest
  作者：Mohammad Hossein Tootoonchi、Gaurav Sharma、Jonathan Calles、Rajeev Prabhakar、Angel E. Kaifer

  DOI：10.1002/anie.201606038

  日期：2016.9.12

  The self‐assembly in aqueous solution of the well‐known cyclophane, cyclobis(paraquat‐p‐phenylene) (BB4+), and two cucurbit[7]uril (CB7) hosts around a simple hydroquinol‐based, diamine guest (GH22+) was investigated by 1H NMR and electronic absorption spectroscopies, electrospray mass spectrometry and DFT computations. The formation of a quaternary supramolecular assembly [GH22+⋅BB4+⋅ (CB7)2] was

  著名的环烷，环双（百草枯-对苯撑）（BB 4+）和两个葫芦[7]尿素（CB7）在水溶液中的自组装围绕着一个简单的基于对苯二酚的二胺客体（GH）通过1 H NMR和电子吸收光谱，电喷雾质谱和DFT计算研究2 2+）。四元超分子组装体的形成[GH 2 2 + ⋅BB4 + ⋅（CB7）2结果表明，这是一个非常有效的过程，这不仅是由于主机和宾客之间的吸引力所致，而且还因为最终组件中主机之间的横向相互作用。这种相互补充的有吸引力的相互作用导致清晰的协作结合效果，有助于克服多组分组装的熵障。
• Quantifying the barrier for the movement of cyclobis(paraquat-<i>p</i>-phenylene) over the dication of monopyrrolotetrathiafulvalene
  作者：Rikke Kristensen、Mathias S. Neumann、Sissel S. Andersen、Paul C. Stein、Amar H. Flood、Jan O. Jeppesen

  DOI：10.1039/d1ob02263f

  日期：——

  A bistable [2]pseudorotaxane 1⊂CBPQT·4PF6 and a bistable [2]rotaxane 2·4PF6 have been synthesised to measure the height of an electrostatic barrier produced by double molecular oxidation (0 to +2). Both systems have monopyrrolotetrathiafulvalene (MPTTF) and oxyphenylene (OP) as stations for cyclobis(paraquat-p-phenylene) (CBPQT4+). They have a large stopper at one end while the second stopper in 24+

  已经合成了双稳态[2]假轮烷1 ⊂CBPQT·4PF 6和双稳态[2]轮烷2 ·4PF 6来测量由双分子氧化（0到+2）产生的静电势垒的高度。两个系统都有单吡咯并四硫富瓦烯 (MPTTF) 和氧亚苯基 (OP) 作为环双(百草枯-对亚苯基) (CBPQT 4+ ) 的站点。它们的一端有一个大的塞子，而2 4+中的第二个塞子由硫乙基 (SEt) 基团和硫代二甘醇 (TDEG) 取代基组成，而1 ⊂CBPQT 4+, SEt 基团已被体积较小的硫甲基 (SMe) 基团取代。当比较两个系统的物理性质时，MPTTF 单元上取代基的这种看似很小的差异导致了深刻的变化，从而允许首次测量 CBPQT 4+环在 [2] 假轮烷中 MPTTF 2+单元上的脱滑. 采用循环伏安法和1 H NMR 谱研究了1 ⊂CBPQT·MPTTF 4+和2 ·MPTTF 4+的转换机理，发现 CBPQT 4+首先移动到 OP
• Artificial Molecular Pump Operating in Response to Electricity and Light
  作者：Qing-Hui Guo、Yunyan Qiu、Xinyi Kuang、Jiaqi Liang、Yuanning Feng、Long Zhang、Yang Jiao、Dengke Shen、R. Dean Astumian、J. Fraser Stoddart

  DOI：10.1021/jacs.0c06663

  日期：2020.8.26

  essential for the development of molecular nanotechnology. The advent of mechanically interlocked molecules (MIMs) has enhanced significantly the opportunities for chemists to harness such motions in artificial molecular machines (AMMs). Recently, we have developed artificial molecular pumps (AMPs) capable of producing highly energetic oligo- and polyrotaxanes with high precision. Here, we report the design

  控制分子中组成部分相对运动的能力对于分子纳米技术的发展至关重要。机械互锁分子 (MIM) 的出现大大增加了化学家在人工分子机器 (AMM) 中利用此类运动的机会。最近，我们开发了能够高精度生产高能低聚轮烷和聚轮烷的人工分子泵 (AMP)。在这里，我们报告了一个 AMP 的设计、合成和操作，该 AMP 包含一个允许使用正交刺激的可光裂解塞子。我们的方法采用棘轮机制将环泵送到收集链上，形成中间 [2] 轮烷。在随后的时间，光的应用触发环的释放回到具有时间控制的本体溶液中。该过程通过萘基荧光团的荧光猝灭来监测。这种设计可以应用于制造具有按需功能的分子传输系统。
• Reversible conversion between a pleated oligo-tetrathiafulvalene radical foldamer and folded donor–acceptor [3]pseudorotaxane under redox conditions
  作者：Tian-Guang Zhan、Lin Wu、Zhixiong Zhao、Zhi-Bei Zhou、Meng-Yan Yun、Jie Wei、Si-Tai Zheng、Huan-Huan Yin、Kang-Da Zhang

  DOI：10.1039/c7cc02526b

  日期：——

  Linear tetrathiafulvalene (TTF) oligomers were synthesized, which could not only form pleated TTF radical cation foldamer under oxidation condition, but also interlocked with CBPQT4+ to form folded donor-acceptor [3]pseudorotaxane in the netrual state of TTF. Moreover, switchable transformation between these two folded supramolecular structures was achieved under the alternative regulation of the redox

  合成了线性四硫富瓦烯（TTF）低聚物，它不仅可以在氧化条件下形成折叠的TTF自由基阳离子折叠剂，而且可以与CBPQT4 +互锁形成折叠的供体-受体[3]伪轮烷，处于TTF的净态。而且，在TTF单元的氧化还原状态的替代性调节下，在这两个折叠的超分子结构之间实现了可转换的转变。