Sequence-defined main-chain photoswitching macromolecules with odd-even effect-controlled properties

IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Chem Pub Date : 2024-11-04 DOI:10.1016/j.chempr.2024.10.008
Linh Duy Thai, Jochen A. Kammerer, Dmitri Golberg, Hatice Mutlu, Christopher Barner-Kowollik
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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.

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具有奇偶效应控制特性的序列定义主链光开关大分子
在聚合物主链中加入刺激响应分子可最大限度地提高聚合物的刺激响应。然而,这种复杂大分子的简便正交合成是一项艰巨的挑战,尤其是在实现绝对的链端基团保真度、单分散性和形成嵌段共聚物(BCP)方面。我们利用无金属羟基-炔单击和脱保护化学来实现单分散、序列确定的低聚物和 BCP,其特点是以α-二亚胺作为主链光开关,并正交加入功能性末端基团(烯烃、丙烯酸酯和非活化炔)。我们揭示了序列对溶液和固态材料特性的重大影响,表现为对流体力学体积、玻璃化转变温度和 BCP 域间距的强烈奇偶效应。奇偶效应源于我们精确的合成策略所产生的序列的独特对称性。因此,我们的序列定义正交合成策略具有近乎绝对的链端组保真度和广泛的官能团兼容性,为实现具有精确性质、拓扑结构、组成和主链功能的复杂聚合物材料铺平了道路。
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来源期刊
Chem
Chem Environmental Science-Environmental Chemistry
CiteScore
32.40
自引率
1.30%
发文量
281
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.
期刊最新文献
De novo luciferases enable multiplexed bioluminescence imaging One-pot catalytic conversion of polyethylene wastes to gasoline through a dual-catalyst system New light on proton transfer: Spectral and kinetic signature of a transient Eigen complex Sequence-defined main-chain photoswitching macromolecules with odd-even effect-controlled properties Direct production of o-xylene from six-component BTEXs using a channel-pore interconnected metal-organic framework
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