Linh Duy Thai, Jochen A. Kammerer, Dmitri Golberg, Hatice Mutlu, Christopher Barner-Kowollik
{"title":"Sequence-defined main-chain photoswitching macromolecules with odd-even effect-controlled properties","authors":"Linh Duy Thai, Jochen A. Kammerer, Dmitri Golberg, Hatice Mutlu, Christopher Barner-Kowollik","doi":"10.1016/j.chempr.2024.10.008","DOIUrl":null,"url":null,"abstract":"The installation of stimuli-responsive moieties into their main chain maximizes the stimuli response of polymers. Yet, facile and orthogonal synthesis of such complex macromolecules is a daunting challenge, especially for achieving absolute chain-end-group fidelity, monodispersity, and the formation of block copolymers (BCPs). We harness metal-free hydroxyl-yne click and deprotection chemistry to realize monodisperse, sequence-defined oligomers and BCPs featuring α-bisimines as main-chain photoswitches and orthogonally incorporate functional terminal groups (olefins, acrylates, and non-activated alkynes). We reveal the significant influence of the sequence on solution and solid-state material properties, which manifests as a strong odd-even effect on the hydrodynamic volume, glass transition temperature, and BCP domain spacing. The odd-even effect originates from the distinct symmetries of the sequences resulting from our precise synthetic strategy. Thus, our sequence-defined, orthogonal synthesis strategy with near absolute chain-end-group fidelity and wide functional group compatibility paves the way toward complex polymeric materials with precise properties, topology, composition, and main-chain functionalities.","PeriodicalId":268,"journal":{"name":"Chem","volume":null,"pages":null},"PeriodicalIF":19.1000,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1016/j.chempr.2024.10.008","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The installation of stimuli-responsive moieties into their main chain maximizes the stimuli response of polymers. Yet, facile and orthogonal synthesis of such complex macromolecules is a daunting challenge, especially for achieving absolute chain-end-group fidelity, monodispersity, and the formation of block copolymers (BCPs). We harness metal-free hydroxyl-yne click and deprotection chemistry to realize monodisperse, sequence-defined oligomers and BCPs featuring α-bisimines as main-chain photoswitches and orthogonally incorporate functional terminal groups (olefins, acrylates, and non-activated alkynes). We reveal the significant influence of the sequence on solution and solid-state material properties, which manifests as a strong odd-even effect on the hydrodynamic volume, glass transition temperature, and BCP domain spacing. The odd-even effect originates from the distinct symmetries of the sequences resulting from our precise synthetic strategy. Thus, our sequence-defined, orthogonal synthesis strategy with near absolute chain-end-group fidelity and wide functional group compatibility paves the way toward complex polymeric materials with precise properties, topology, composition, and main-chain functionalities.
期刊介绍:
Chem, affiliated with Cell as its sister journal, serves as a platform for groundbreaking research and illustrates how fundamental inquiries in chemistry and its related fields can contribute to addressing future global challenges. It was established in 2016, and is currently edited by Robert Eagling.