Das Angshuman, Ghosh Saikat, George Subi J
New Chemistry Unit and School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore, 560064, India.
Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202413747. doi: 10.1002/anie.202413747. Epub 2024 Oct 18.
The amplification of asymmetry in supramolecular polymers has recently garnered significant attention. While asymmetry amplification has predominantly been explored under thermodynamic conditions, the kinetic aspect of this process unveils intriguing observations, yet is scarcely reported in the literature. Herein, drawing inspiration from macromolecular systems, we propose a novel strategy for enhancing asymmetry in supramolecular polymers through a seed-induced supramolecular polymerization approach under kinetic conditions, employing a naphthalene diimide-derived monomer (ANSG) for template-induced supramolecular polymerization, utilizing adenosine triphosphate (ATP) and pyrophosphate (PPi) as templates. A chiral seed comprising [ANSG-ATP] effectively amplifies the overall supramolecular asymmetry when exposed to a mixture of achiral templates (PPi) and monomers (ANSG), owing to its efficient seeding characteristics under kinetic conditions. As a result of efficient co-operativity, conversely, employing an achiral seed [ANSG-PPi] in a mixture of chiral templates (ATP) and monomers (ANSG) results in the attenuation of asymmetry, highlighting the effective modulation achievable through the seeding approach, an unprecedented observation in the field. Exploiting the efficient aggregation-induced emission enhancement (AIEE) of the resultant supramolecular polymers further extends the amplification and attenuation of circularly polarized luminescence (CPL) as a potential function.
超分子聚合物中不对称性的放大最近引起了广泛关注。虽然不对称性放大主要是在热力学条件下进行研究的,但该过程的动力学方面揭示了有趣的现象,然而在文献中却鲜有报道。在此,受大分子体系的启发,我们提出了一种新策略,即在动力学条件下通过种子诱导的超分子聚合方法增强超分子聚合物的不对称性,采用萘二酰亚胺衍生的单体(ANSG)进行模板诱导的超分子聚合,利用三磷酸腺苷(ATP)和焦磷酸(PPi)作为模板。当暴露于非手性模板(PPi)和单体(ANSG)的混合物中时,由[ANSG-ATP]组成的手性种子因其在动力学条件下的有效种子特性而有效地放大了整体超分子不对称性。相反,由于高效的协同作用,在手性模板(ATP)和单体(ANSG)的混合物中使用非手性种子[ANSG-PPi]会导致不对称性减弱,突出了通过种子方法可实现的有效调控,这在该领域是前所未有的观察结果。利用所得超分子聚合物的高效聚集诱导发光增强(AIEE)进一步扩展了圆偏振发光(CPL)作为潜在功能的放大和衰减。