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Supramolecular Depolymerization in the Mixture of Two Poor Solvents: Mechanistic Insights and Modulation of Supramolecular Polymerization of Ionic π‐Systems
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-11-28 , DOI: 10.1002/anie.202011977 Srinu Kotha 1 , Mathijs F. J. Mabesoone 2 , Dasari Srideep 1 , Rahul Sahu 3 , Sandeep K. Reddy 3 , Kotagiri Venkata Rao 1
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-11-28 , DOI: 10.1002/anie.202011977 Srinu Kotha 1 , Mathijs F. J. Mabesoone 2 , Dasari Srideep 1 , Rahul Sahu 3 , Sandeep K. Reddy 3 , Kotagiri Venkata Rao 1
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Solvents are fundamentally essential for the synthesis and processing of soft materials. Supramolecular polymers (SPs), an emerging class of soft materials, are usually stable in single and mixtures of poor solvents. In contrast to these preconceived notions, here we report the depolymerization of SPs in the mixture of two poor solvents. This surprising behavior was observed for well‐known cationic perylene diimides (cPDIs) in the mixtures of water and amphiphilic organic solvents such as isopropanol (IPA). cPDIs form stable SPs in water and IPA but readily depolymerize into monomers in 50–70 vol% IPA containing water. This is due to the selective solvation of the π‐surface of cPDIs by alkyl chains of IPA and ionic side chains by water, as evidenced by molecular dynamic simulations. Moreover, by systematically changing the ratio between water and amphiphilic organic solvent, we could achieve an unprecedented supramolecular polymerization both by increasing and decreasing the solvent polarity.
中文翻译：
两种不良溶剂的混合物中的超分子解聚：离子π系统超分子聚合的机理研究和调节
溶剂对于软质材料的合成和加工至关重要。超分子聚合物（SPs）是一类新兴的软材料，通常在单一溶剂和不良溶剂的混合物中都稳定。与这些先入为主的概念相反，在这里我们报告了在两种不良溶剂的混合物中SP的解聚。在水和两亲有机溶剂（如异丙醇（IPA））的混合物中，众所周知的阳离子per二酰亚胺（c PDIs）观察到了这种令人惊讶的行为。c PDI在水和IPA中形成稳定的SP，但很容易在50-70％（体积）的IPA水中解聚为单体。这是由于c PDI的π表面的选择性溶剂化分子动力学模拟证明，IPA的烷基链和水的离子性侧链都可以。此外，通过系统地改变水与两亲性有机溶剂之间的比例，我们可以通过增加和减少溶剂极性来实现前所未有的超分子聚合。
更新日期：2020-11-28
中文翻译：
两种不良溶剂的混合物中的超分子解聚：离子π系统超分子聚合的机理研究和调节
溶剂对于软质材料的合成和加工至关重要。超分子聚合物（SPs）是一类新兴的软材料，通常在单一溶剂和不良溶剂的混合物中都稳定。与这些先入为主的概念相反，在这里我们报告了在两种不良溶剂的混合物中SP的解聚。在水和两亲有机溶剂（如异丙醇（IPA））的混合物中，众所周知的阳离子per二酰亚胺（c PDIs）观察到了这种令人惊讶的行为。c PDI在水和IPA中形成稳定的SP，但很容易在50-70％（体积）的IPA水中解聚为单体。这是由于c PDI的π表面的选择性溶剂化分子动力学模拟证明，IPA的烷基链和水的离子性侧链都可以。此外，通过系统地改变水与两亲性有机溶剂之间的比例，我们可以通过增加和减少溶剂极性来实现前所未有的超分子聚合。
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