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包含紫罗精阳离子自由基和 CB[8]的二维超分子有机骨架的可逆性。

Reversible 2D Supramolecular Organic Frameworks encompassing Viologen Cation Radicals and CB[8].

机构信息

Electroorganic Division, CSIR-Central Electrochemical Research Institute, Karaikudi, 630003, Tamil Nadu, India.

Academy of Scientific and Innovative Research (AcSIR), CSIR-Central Electrochemical Research Institute, Karaikudi, 630003, Tamil Nadu, India.

出版信息

Sci Rep. 2018 Jan 22;8(1):1354. doi: 10.1038/s41598-018-19739-7.

Abstract

Reversible 2D supramolecular organic frameworks encompassing branched viologen architectures and cucurbit[8]uril (CB[8]) were constructed and investigated. UV-vis investigation clearly indicates the formation and intermolecular dimerization of monocation radicals and their encapsulation into the hydrophobic CB[8] cavity which is further complemented by EPR (electron paramagnetic resonance) spectroscopy. Particle size measurements by dynamic light scattering method showed particle sizes in the range of several µm indicating larger aggregates. Zeta potential measurements suggested the instability of these particles and their tendency to form aggregates. TEM (transmission electron microscope) analysis further revealed the formation of supramolecular polymer (monocation radical with cucurbit[8]uril) whose diameter were in the range of several µm as indicated by DLS measurements; however the oxidized form, i.e., the viologen dication with cucurbit[8]uril showed dotted spots in the range of sub nanometer level. The internal periodicities of the supramolecular polymers were analyzed by SAXs (small angle X-ray scattering) measurements. Additionally, we have demonstrated that these supramolecular organic frameworks can be depolymerized by oxidation in air and again can be polymerized (intermolecular radical dimerization) by reduction under inert atmosphere demonstrating that these systems will be of broad interest.

摘要

构建并研究了包含支化紫精结构和葫芦[8]脲(CB[8])的可还原二维超分子有机框架。紫外可见光谱研究清楚地表明了单阳离子自由基的形成和分子间二聚体及其包封到疏水 CB[8]腔中的情况,这进一步得到了电子顺磁共振(EPR)光谱的补充。动态光散射法的粒径测量表明粒径在几微米范围内,表明存在较大的聚集体。Zeta 电位测量表明这些颗粒不稳定,并且它们有形成聚集体的趋势。TEM(透射电子显微镜)分析进一步揭示了超分子聚合物(带葫芦[8]脲的单阳离子自由基)的形成,其直径在几微米范围内,如 DLS 测量所示;然而,氧化形式,即带葫芦[8]脲的紫精二阳离子显示出亚纳米级范围内的点状斑点。超分子聚合物的内部周期性通过 SAXs(小角 X 射线散射)测量进行了分析。此外,我们已经证明,这些超分子有机框架可以通过空气中的氧化解聚,并且可以在惰性气氛下通过还原再次聚合(分子间自由基二聚体),证明这些系统将具有广泛的兴趣。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ae6d/5778010/39a156ad7d7d/41598_2018_19739_Fig1_HTML.jpg

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