Sculpting the tunable mesoscopic helical chirality into poly(m-phenylenediamine)via Mn^(2+)coordination  

锰离子配位构筑聚间苯二胺的可控介观螺旋手性

作　　者：Xinlin Zha Mengjuan Zuo Haining You Zhong Yan Yi Xiong Ying Liu Liu Liu Yi Wu Ke Liu Mufang Li Tao Zhao Dong Wang 查新林;左梦娟;尤海宁;严忠;熊祎;刘英;刘柳;武艺;刘轲;李沐芳;赵涛;王栋(College of Chemistry and Chemical Engineering,Donghua University,Shanghai 201620,China;Key Laboratory of Textile Fiber and Products,Ministry of Education,Wuhan Textile University,Wuhan 430200,China)

机构地区：[1]College of Chemistry and Chemical Engineering,Donghua University,Shanghai 201620,China [2]Key Laboratory of Textile Fiber and Products,Ministry of Education,Wuhan Textile University,Wuhan 430200,China

出　　处：《Science China Materials》2024年第10期3330-3338,共9页中国科学（材料科学）（英文版）

基　　金：supported by the National Natural Science Foundation of China(U20A20257);the National Key Research and Development Program of China(2022YFB3805803).

摘　　要：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 Mn^(2+)and chiral phenylglycine derivatives(L-/D-16PhgCOOH)as templates,using m-phenylenediamine as the monomer to synthesize chiral poly(m-phenylenediamine)(PMPD).In the Mn^(2+)-templated system,the PMPD’s handedness is opposite to the molecular chirality of L-/D-16PhgCOOH,while in the Mn^(2+)-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 Mn^(2+)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.展现可控介观螺旋性的手性共轭聚合物在对映体分离和不对称催化等领域引起了广泛关注.然而,如何以高效的方式实现按需手性和良好的加工性仍然是个挑战.在本工作中,我们利用Mn^(2+)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,间苯二胺为单体,合成了手性聚间苯二胺(PMPD).在Mn^(2+)体系中,所得PMPD的介观螺旋性与L-/D-16PhgCOOH的分子手性相反;而在无Mn^(2+)体系中,PMPD的介观螺旋性与模板的分子手性一致.该策略可以在对映体纯的模板分子体系中制备出具有可切换螺旋性的手性PMPD.Mn^(2+)的引入被证实打破并重构了共组装体中的超分子相互作用,影响了后续的超分子堆积模式.通过对上述所得PMPD进行碳化也得到了具有手性光学活性的氮掺杂碳纳米材料,这些碳材料良好地继承了原始PMPD的介观螺旋性.此外,将F-127引入至聚合体系可增大PMPD的长径比,利用传统抽滤及冷冻干燥工艺首次制备出由介观螺旋单元构成的自支撑二维薄膜和三维泡沫.鉴于该手性共轭聚合物及其相应的碳纳米材料中存在丰富的Lewis碱基锚定位点,它们有望成为构建新型手性宿主-客体相互作用的多功能平台.该研究为高效制备和加工具有可控螺旋性的手性共轭聚合物开辟了新途径.

关 键 词：helical conjugated polymers Mn^(2+)coordination chirality inversion chiral carbonaceous nanotubes 

分 类 号：O641.3[理学—物理化学]