Kotha Srinu, Sahu Rahul, Yadav Aditya Chandrakant, Sharma Preeti, Kumar B V V S Pavan, Reddy Sandeep K, Rao Kotagiri Venkata
Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi, Sangareddy, Telangana, 502284, India.
Centre for Computational and Data Science, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal, 721302, India.
Nat Commun. 2024 Apr 30;15(1):3672. doi: 10.1038/s41467-024-47874-5.
The synthesis of supramolecular polymers with controlled architecture is a grand challenge in supramolecular chemistry. Although living supramolecular polymerization via primary nucleation has been extensively studied for controlling the supramolecular polymerization of small molecules, the resulting supramolecular polymers have typically exhibited one-dimensional morphology. In this report, we present the synthesis of intriguing supramolecular polymer architectures through a secondary nucleation event, a mechanism well-established in protein aggregation and the crystallization of small molecules. To achieve this, we choose perylene diimide with 2-ethylhexyl chains at the imide position as they are capable of forming dormant monomers in solution. Activating these dormant monomers via mechanical stimuli and hetero-seeding using propoxyethyl perylene diimide seeds, secondary nucleation event takes over, leading to the formation of three-dimensional spherical spherulites and scarf-like supramolecular polymer heterostructures, respectively. Therefore, the results presented in this study propose a simple molecular design for synthesizing well-defined supramolecular polymer architectures via secondary nucleation.
合成具有可控结构的超分子聚合物是超分子化学中的一项重大挑战。尽管通过初级成核进行的活性超分子聚合已被广泛研究用于控制小分子的超分子聚合，但所得的超分子聚合物通常呈现一维形态。在本报告中，我们通过二次成核事件展示了有趣的超分子聚合物结构的合成，二次成核是一种在蛋白质聚集和小分子结晶中已确立的机制。为实现这一点，我们选择在酰亚胺位置带有2-乙基己基链的苝二酰亚胺，因为它们能够在溶液中形成休眠单体。通过机械刺激激活这些休眠单体，并使用丙氧基乙基苝二酰亚胺晶种进行异质成核，二次成核事件随之发生，分别导致形成三维球形球晶和围巾状超分子聚合物异质结构。因此，本研究结果提出了一种通过二次成核合成明确超分子聚合物结构的简单分子设计。
