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

被引:0
作者
Thai, Linh Duy [1 ,2 ,3 ]
Kammerer, Jochen A. [1 ,2 ]
Golberg, Dmitri [1 ,2 ]
Mutlu, Hatice [4 ]
Barner-Kowollik, Christopher [1 ,2 ,3 ]
机构
[1] Queensland Univ Technol QUT, Sch Chem & Phys, 2 George St, Brisbane, Qld 4000, Australia
[2] Queensland Univ Technol QUT, Ctr Mat Sci, 2 George St, Brisbane, Qld 4000, Australia
[3] Karlsruhe Inst Technol KIT, Inst Nanotechnol INT, Hermann von Helmholtz Pl 1, D-76344 Eggenstein Leopoldshafen, Germany
[4] Univ Haute Alsace, Inst Sci Mat Mulhouse, CNRS, UMR 7361, 15 Rue Jean Starcky, F-68057 Mulhouse, France
来源
CHEM | 2025年 / 11卷 / 02期
基金
澳大利亚研究理事会;
关键词
SIZE-EXCLUSION CHROMATOGRAPHY; RESPONSIVE POLYMERS; MOLECULAR-WEIGHT; PHASE-BEHAVIOR; BLOCK; DISPERSITY; POLYDISPERSITY;
D O I
10.1016/j.chempr.2024.10.008
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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 a-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.
引用
收藏
页数:13
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