{"title":"铝介导的烯丙基醯胺聚合,生成具有增强非传统本征发光特性的α,ω-官能化 C3 聚合物","authors":"Tongyao Zhao, Mingyi Liao*, Yanming Hu, Guangyuan Zhou, Pibo Liu* and Nikos Hadjichristidis, ","doi":"10.1021/acs.macromol.3c02516","DOIUrl":null,"url":null,"abstract":"<p >Allylic ylide polymerization is an unconventional method for synthesizing polymers with unique allylic repeat units. However, in contrast to significant efforts to develop new monomers, the development of new catalysts for this realm is scarce. Thus far, only organoboranes have been explored and proven to be efficient catalysts. Here, we demonstrate that aluminum-based catalysts, triethylaluminum (AlEt<sub>3</sub>), aluminum chloride (AlCl<sub>3</sub>), and aluminum bromide (AlBr<sub>3</sub>), are efficient for 2-methylallyl triphenyl arsonium ylide polymerization, affording poly(propenylenes) with high 1,3-monomeric insertion selectivity (>97.7%) and <i>trans</i>-configuration (>92.5%). The aluminum-mediated polymerizations proceed in an immortal manner, as evidenced by the controlled molecular weights (DP<sub>NMR</sub>), narrow polydispersities, and chain extension experiments. Interestingly, in the AlEt<sub>3</sub>-mediated polymerization, each Al atom produces three polymer chains, whereas in the cases of aluminum halides, one polymer chain per Al atom is observed due to the weak migration ability of halogen. On the basis of experimental results, an aluminum-mediated ylide polymerization mechanism is proposed. This mechanism involves halogen and [1,3]-aluminum migrations, which dictate the catalyst activity and product structures. Moreover, all C3 polymers exhibit nontraditional intrinsic luminescence. Incorporation of halogen atoms at the chain end significantly enhances the photoluminescence properties due to the improved stacking of polymeric segments through halogen-π interactions. This study presents a new approach for synthesizing α,ω-end-functionalized C3 polymers and also expands the potential for the rational design of efficient catalysts for ylide polymerizations.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Aluminum-Mediated Polymerization of Allylic Ylides toward α,ω-Functionalized C3 Polymers with Enhanced Nontraditional Intrinsic Luminescence\",\"authors\":\"Tongyao Zhao, Mingyi Liao*, Yanming Hu, Guangyuan Zhou, Pibo Liu* and Nikos Hadjichristidis, \",\"doi\":\"10.1021/acs.macromol.3c02516\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Allylic ylide polymerization is an unconventional method for synthesizing polymers with unique allylic repeat units. However, in contrast to significant efforts to develop new monomers, the development of new catalysts for this realm is scarce. Thus far, only organoboranes have been explored and proven to be efficient catalysts. Here, we demonstrate that aluminum-based catalysts, triethylaluminum (AlEt<sub>3</sub>), aluminum chloride (AlCl<sub>3</sub>), and aluminum bromide (AlBr<sub>3</sub>), are efficient for 2-methylallyl triphenyl arsonium ylide polymerization, affording poly(propenylenes) with high 1,3-monomeric insertion selectivity (>97.7%) and <i>trans</i>-configuration (>92.5%). The aluminum-mediated polymerizations proceed in an immortal manner, as evidenced by the controlled molecular weights (DP<sub>NMR</sub>), narrow polydispersities, and chain extension experiments. Interestingly, in the AlEt<sub>3</sub>-mediated polymerization, each Al atom produces three polymer chains, whereas in the cases of aluminum halides, one polymer chain per Al atom is observed due to the weak migration ability of halogen. On the basis of experimental results, an aluminum-mediated ylide polymerization mechanism is proposed. This mechanism involves halogen and [1,3]-aluminum migrations, which dictate the catalyst activity and product structures. Moreover, all C3 polymers exhibit nontraditional intrinsic luminescence. Incorporation of halogen atoms at the chain end significantly enhances the photoluminescence properties due to the improved stacking of polymeric segments through halogen-π interactions. This study presents a new approach for synthesizing α,ω-end-functionalized C3 polymers and also expands the potential for the rational design of efficient catalysts for ylide polymerizations.</p>\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-06-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.macromol.3c02516\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.macromol.3c02516","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Aluminum-Mediated Polymerization of Allylic Ylides toward α,ω-Functionalized C3 Polymers with Enhanced Nontraditional Intrinsic Luminescence
Allylic ylide polymerization is an unconventional method for synthesizing polymers with unique allylic repeat units. However, in contrast to significant efforts to develop new monomers, the development of new catalysts for this realm is scarce. Thus far, only organoboranes have been explored and proven to be efficient catalysts. Here, we demonstrate that aluminum-based catalysts, triethylaluminum (AlEt3), aluminum chloride (AlCl3), and aluminum bromide (AlBr3), are efficient for 2-methylallyl triphenyl arsonium ylide polymerization, affording poly(propenylenes) with high 1,3-monomeric insertion selectivity (>97.7%) and trans-configuration (>92.5%). The aluminum-mediated polymerizations proceed in an immortal manner, as evidenced by the controlled molecular weights (DPNMR), narrow polydispersities, and chain extension experiments. Interestingly, in the AlEt3-mediated polymerization, each Al atom produces three polymer chains, whereas in the cases of aluminum halides, one polymer chain per Al atom is observed due to the weak migration ability of halogen. On the basis of experimental results, an aluminum-mediated ylide polymerization mechanism is proposed. This mechanism involves halogen and [1,3]-aluminum migrations, which dictate the catalyst activity and product structures. Moreover, all C3 polymers exhibit nontraditional intrinsic luminescence. Incorporation of halogen atoms at the chain end significantly enhances the photoluminescence properties due to the improved stacking of polymeric segments through halogen-π interactions. This study presents a new approach for synthesizing α,ω-end-functionalized C3 polymers and also expands the potential for the rational design of efficient catalysts for ylide polymerizations.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.