Hua Lin, Xiuying Wu, Ziheng Lin, Rongrong Hu* and Ben Zhong Tang,
{"title":"芳香胺、醛和炔的不对称多组分聚合反应,实现手性聚(丙炔胺)和骨架转化","authors":"Hua Lin, Xiuying Wu, Ziheng Lin, Rongrong Hu* and Ben Zhong Tang, ","doi":"10.1021/acs.chemmater.4c00534","DOIUrl":null,"url":null,"abstract":"<p >The construction of functional chiral polymers with newly built chiral centers from entire achiral monomers is charming but challenging in chiral material science. In this work, an asymmetric multicomponent polymerization (<i>a</i>MCP) of aromatic primary amines, aromatic aldehydes, and alkynes was developed with the catalysis of CuOTf-pybox complex to produce chiral poly(propargylamine)s. The supramolecular interactions between the CuOTf-pybox complex and the reactive species not only assisted the formation of a preorganized intermediate state to induce stereoselective reaction to produce chiral polymers but also reduced the reaction-activated energy to enable efficient A<sup>3</sup>-polycoupling at room temperature, affording chiral poly(propargylamine)s with high yields (up to 96%), high molecular weights (<i>M</i><sub>n</sub>s up to 44 800 g/mol), significant circular dichroism signal, good solubility, and high thermal stability. Moreover, the unique chiral aromatic poly(propargylamine)s with remaining N–H moieties enabled complete conversion to a new group of chiral polyheterocycles, poly(thiazolidine-2-imine)s with elongated conjugation and enhanced fluorescence, realizing polymer backbone transformation through facile reaction with benzoyl isothiocyanate. The <i>a</i>MCP has provided an efficient and convenient approach for the construction of chiral polymers with diversified structures from simple achiral monomers and may accelerate the development of chiral polymer materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Asymmetric Multicomponent Polymerizations of Aromatic Amines, Aldehydes, and Alkynes Toward Chiral Poly(propargylamine)s and the Backbone Transformation\",\"authors\":\"Hua Lin, Xiuying Wu, Ziheng Lin, Rongrong Hu* and Ben Zhong Tang, \",\"doi\":\"10.1021/acs.chemmater.4c00534\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The construction of functional chiral polymers with newly built chiral centers from entire achiral monomers is charming but challenging in chiral material science. In this work, an asymmetric multicomponent polymerization (<i>a</i>MCP) of aromatic primary amines, aromatic aldehydes, and alkynes was developed with the catalysis of CuOTf-pybox complex to produce chiral poly(propargylamine)s. The supramolecular interactions between the CuOTf-pybox complex and the reactive species not only assisted the formation of a preorganized intermediate state to induce stereoselective reaction to produce chiral polymers but also reduced the reaction-activated energy to enable efficient A<sup>3</sup>-polycoupling at room temperature, affording chiral poly(propargylamine)s with high yields (up to 96%), high molecular weights (<i>M</i><sub>n</sub>s up to 44 800 g/mol), significant circular dichroism signal, good solubility, and high thermal stability. Moreover, the unique chiral aromatic poly(propargylamine)s with remaining N–H moieties enabled complete conversion to a new group of chiral polyheterocycles, poly(thiazolidine-2-imine)s with elongated conjugation and enhanced fluorescence, realizing polymer backbone transformation through facile reaction with benzoyl isothiocyanate. The <i>a</i>MCP has provided an efficient and convenient approach for the construction of chiral polymers with diversified structures from simple achiral monomers and may accelerate the development of chiral polymer materials.</p>\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-06-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00534\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00534","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Asymmetric Multicomponent Polymerizations of Aromatic Amines, Aldehydes, and Alkynes Toward Chiral Poly(propargylamine)s and the Backbone Transformation
The construction of functional chiral polymers with newly built chiral centers from entire achiral monomers is charming but challenging in chiral material science. In this work, an asymmetric multicomponent polymerization (aMCP) of aromatic primary amines, aromatic aldehydes, and alkynes was developed with the catalysis of CuOTf-pybox complex to produce chiral poly(propargylamine)s. The supramolecular interactions between the CuOTf-pybox complex and the reactive species not only assisted the formation of a preorganized intermediate state to induce stereoselective reaction to produce chiral polymers but also reduced the reaction-activated energy to enable efficient A3-polycoupling at room temperature, affording chiral poly(propargylamine)s with high yields (up to 96%), high molecular weights (Mns up to 44 800 g/mol), significant circular dichroism signal, good solubility, and high thermal stability. Moreover, the unique chiral aromatic poly(propargylamine)s with remaining N–H moieties enabled complete conversion to a new group of chiral polyheterocycles, poly(thiazolidine-2-imine)s with elongated conjugation and enhanced fluorescence, realizing polymer backbone transformation through facile reaction with benzoyl isothiocyanate. The aMCP has provided an efficient and convenient approach for the construction of chiral polymers with diversified structures from simple achiral monomers and may accelerate the development of chiral polymer materials.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.