Jalani Krishnendu, Das Anjali Devi, Sasmal Ranjan, Agasti Sarit S, George Subi J
Supramolecular Chemistry Laboratory, New Chemistry Unit, School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore, 560064, India.
New Chemistry Unit & Chemistry & Physics of Materials Unit, School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Bangalore, Karnataka, 560064, India.
Nat Commun. 2020 Aug 7;11(1):3967. doi: 10.1038/s41467-020-17799-w.
Temporally controlled cooperative and living supramolecular polymerization by the buffered release of monomers has been recently introduced as an important concept towards obtaining monodisperse and multicomponent self-assembled materials. In synthetic, dynamic supramolecular polymers, this requires efficient design strategies for the dormant, inactive states of the monomers to kinetically retard the otherwise spontaneous nucleation process. However, a generalized design principle for the dormant monomer states to expand the scope of precision supramolecular polymers has not been established yet, due to the enormous differences in the mechanism, energetic parameters of self-assembly and monomer exchange dynamics of the diverse class of supramolecular polymers. Here we report the concept of transient dormant states of monomers generated by redox reactions as a predictive general design to achieve monodisperse supramolecular polymers of electronically active, chromophoric or donor-acceptor, monomers. The concept has been demonstrated with charge-transfer supramolecular polymers with an alternating donor-acceptor sequence.
最近，通过单体的缓冲释放实现时间控制的协同和活性超分子聚合已作为获得单分散和多组分自组装材料的一个重要概念被引入。在合成的动态超分子聚合物中，这需要针对单体的休眠、非活性状态设计有效的策略，以在动力学上延缓原本自发的成核过程。然而，由于不同类型超分子聚合物在自组装机制、能量参数和单体交换动力学方面存在巨大差异，尚未建立一种通用的设计原则来扩展精确超分子聚合物的范围，从而实现单体休眠状态的设计。在此，我们报告了通过氧化还原反应产生单体瞬态休眠状态的概念，这是一种预测性的通用设计，用于实现具有电子活性、发色或供体 - 受体单体的单分散超分子聚合物。这一概念已通过具有交替供体 - 受体序列的电荷转移超分子聚合物得到验证。
