Sculpting the tunable mesoscopic helical chirality into poly(m-phenylenediamine) via Mn2+ coordination

IF 6.8 2区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Science China Materials Pub Date : 2024-08-06 DOI:10.1007/s40843-024-3033-0

Xinlin Zha (, ), Mengjuan Zuo (, ), Haining You (, ), Zhong Yan (, ), Yi Xiong (, ), Ying Liu (, ), Liu Liu (, ), Yi Wu (, ), Ke Liu (, ), Mufang Li (, ), Tao Zhao (, ), Dong Wang (, )

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Abstract

Chiral conjugated polymers with controlled mesoscopic helicity are gaining attention for enantioseparation and asymmetric catalysis. However, achieving on-demand chirality and processability remain challenging. Herein, we exploit supramolecular coordination polymers formed by Mn²⁺ and chiral phenylglycine derivatives (L-/D-16PhgCOOH) as templates, using m-phenylenediamine as the monomer to synthesize chiral poly(m-phenylenediamine) (PMPD). In the Mn²⁺-templated system, the PMPD’s handedness is opposite to the molecular chirality of L-/D-16PhgCOOH, while in the Mn²⁺-free system, the PMPD handedness aligns with that of the template molecule. This method allows for helicity switching of chiral polymers within a single chirality template system. The introduction of Mn²⁺ is demonstrated to disrupt and reconstitute the supramolecular interactions in the co-assembly, influencing subsequent supramolecular stacking patterns. Carbonizing the resulting PMPDs directly produces chiroptical active nitrogen-doped carbonaceous nanomaterials that inherit the original helicity. Moreover, incorporating F-127 into the polymerization system enhances the aspect ratio of PMPDs, facilitating their delicate processing into chiral self-supporting two-dimensional films and three-dimensional foams. With abundant Lewis basic sites, these chiral polymers offer versatile platforms for novel chiral host-guest interactions.

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通过 Mn2+ 配位雕刻聚间苯二胺的可调介观螺旋手性

在对映体分离和不对称催化方面，具有可控介观螺旋度的手性共轭聚合物正受到越来越多的关注。然而，实现按需手性和可加工性仍然具有挑战性。在此，我们利用 Mn2+ 和手性苯甘氨酸衍生物（L-/D-16PhgCOOH）形成的超分子配位聚合物作为模板，以间苯二胺为单体，合成了手性聚（间苯二胺）（PMPD）。在以 Mn2+ 为模板的体系中，PMPD 的手性与 L-/D-16PhgCOOH 的分子手性相反，而在无 Mn2+ 的体系中，PMPD 的手性与模板分子的手性一致。这种方法可以在单手性模板体系中实现手性聚合物的螺旋度切换。事实证明，引入 Mn2+ 会破坏并重组共组装中的超分子相互作用，从而影响后续的超分子堆叠模式。将生成的 PMPDs 炭化后，可直接生成继承了原始螺旋度的具有iroptical 活性的掺氮碳质纳米材料。此外，在聚合体系中加入 F-127 还能提高 PMPD 的长宽比，便于将其精细加工成手性自支撑二维薄膜和三维泡沫。这些手性聚合物具有丰富的路易斯碱性位点，为新型手性主客体相互作用提供了多功能平台。

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来源期刊

Science China Materials Materials Science-General Materials Science

CiteScore

11.40

自引率

7.40%

发文量

949

期刊介绍： Science China Materials (SCM) is a globally peer-reviewed journal that covers all facets of materials science. It is supervised by the Chinese Academy of Sciences and co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China. The journal is jointly published monthly in both printed and electronic forms by Science China Press and Springer. The aim of SCM is to encourage communication of high-quality, innovative research results at the cutting-edge interface of materials science with chemistry, physics, biology, and engineering. It focuses on breakthroughs from around the world and aims to become a world-leading academic journal for materials science.