New Chemistry Unit and School of Advanced Materials (SAMAt), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore 560064, India.
Department of Innovative Technologies, University of Applied Sciences and Arts of Southern Switzerland, Galleria 2, Via Cantonale 2c, CH-6928 Manno, Switzerland.
J Am Chem Soc. 2020 Apr 22;142(16):7606-7617. doi: 10.1021/jacs.0c01822. Epub 2020 Apr 13.
Multicomponent supramolecular copolymerization promises to construct complex nanostructures with emergent properties. However, even with two monomeric components, various possible outcomes such as self-sorted supramolecular homopolymers, a random (statistical) supramolecular copolymer, an alternate supramolecular copolymer, or a complex supramolecular block copolymer can occur, determined by their intermolecular interactions and monomer exchange dynamics and hence structural prediction is extremely challenging. Herein, we target this challenge and demonstrate unprecedented two-component sequence controlled supramolecular copolymerization by manipulating thermodynamic and kinetic routes in the pathway complexity of self-assembly of the constitutive monomers. Extensive molecular dynamics simulations provided useful mechanistic insights into the monomer exchange rates and free energy of interactions between the monomers that dictate the self-assembly pathway and sequence. The fluorescent nature of core-substituted naphthalene diimide monomers has been further utilized to characterize the three sequences via Structured Illumination Microscopy (SIM).
多组分超分子共聚有望构建具有新兴性质的复杂纳米结构。然而，即使只有两种单体成分，也可能出现各种不同的结果，如自分类超分子均聚物、随机（统计）超分子共聚物、交替超分子共聚物或复杂超分子嵌段共聚物，这取决于它们的分子间相互作用和单体交换动力学，因此结构预测极具挑战性。在此，我们针对这一挑战，通过操纵组成单体自组装路径复杂性中的热力学和动力学途径，展示了前所未有的两成分序列可控超分子共聚。广泛的分子动力学模拟为单体交换率和单体之间相互作用的自由能提供了有用的机理见解，这些因素决定了自组装途径和序列。核取代萘二酰亚胺单体的荧光性质进一步被用于通过结构光照明显微镜（SIM）来表征这三种序列。
