Markiewicz Grzegorz, Smulders Maarten M J, Stefankiewicz Artur R
Faculty of Chemistry Adam Mickiewicz University Uniwersytetu Poznan´skiego 8 61-614 Poznan´ Poland.
Center for Advanced Technologies Adam Mickiewicz University Uniwersytetu Poznan´skiego 10 61-614 Poznan´ Poland.
Adv Sci (Weinh). 2019 Jun 14;6(16):1900577. doi: 10.1002/advs.201900577. eCollection 2019 Aug 21.
Noncovalent self-assembly creates an effective route to highly sophisticated supramolecular polymers with tunable properties. However, the outcome of this assembly process is highly dependent on external conditions. In this work, a monomeric naphthalene diimide (NDI), designed to allow solubility in a wide range of solvents, can assemble into three distinct noncovalent supramolecular species depending on solvent composition and temperature. Namely, while the self-assembly in chlorinated solvents yields relatively short, hydrogen-bonded nanotubes, the reduction of solvent polarity changes the assembly outcome, yielding π-π stacking polymers, which can further bundle into a more complex aggregate. The obtained polymers differ not only in their global morphology but-more strikingly-also in the thermodynamics and kinetics of their supramolecular self-assembly, involving isodesmic or two-stage cooperative assembly with kinetic hysteresis, respectively. Ultimately, three distinct assembly states can be accessed in a single experiment.
非共价自组装为制备具有可调性质的高度复杂超分子聚合物提供了一条有效途径。然而，这种组装过程的结果高度依赖于外部条件。在这项工作中，一种设计成可溶于多种溶剂的单体萘二亚胺（NDI），根据溶剂组成和温度可组装成三种不同的非共价超分子物种。具体而言，在氯化溶剂中的自组装产生相对较短的氢键纳米管，而溶剂极性的降低会改变组装结果，产生π-π堆积聚合物，这种聚合物可进一步聚集成更复杂的聚集体。所得到的聚合物不仅在整体形态上不同，更显著的是在其超分子自组装的热力学和动力学方面也不同，分别涉及等键或具有动力学滞后的两阶段协同组装。最终，在单个实验中可以获得三种不同的组装状态。
