State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200438, China.
Department of Chemistry, Center for Macromolecular Engineering, Carnegie Mellon University, Pittsburgh, PA, 15213, United States.
Nat Commun. 2021 Oct 6;12(1):5853. doi: 10.1038/s41467-021-26186-y.
The regulation of polymer topology and the precise control over the monomer sequence is crucial and challenging in polymer science. Herein, we report an efficient solution-phase synthetic strategy to prepare regio- and sequence-controlled conjugated polymers with topological variations via the usage of methyliminodiacetic acid (MIDA) boronates. Based on the solubility of MIDA boronates and their unusual binary affinity for silica gel, the synthesized regio- and sequence-defined conjugated oligomers can be rapidly purified via precipitation or automatic liquid chromatography. These synthesized discrete oligomers can be used for iterative exponential and sequential growth to obtain linear and dendrimer-like star polymers. Moreover, different topological sequence-controlled conjugated polymers are conveniently prepared from these discrete oligomers via condensation polymerization. By investigating the structure-property relationship of these polymers, we find that the optical properties are strongly influenced by the regiochemistry, which may give inspiration to the design of optoelectronic polymeric materials.
聚合物拓扑结构的调控以及单体序列的精确控制在聚合物科学中至关重要且极具挑战性。在此，我们报告了一种有效的溶液相合成策略，通过使用甲基亚氨基二乙酸（MIDA）硼酸酯来制备具有拓扑变化的区域和序列可控的共轭聚合物。基于 MIDA 硼酸酯的溶解度及其对硅胶的异常二元亲和性，合成的区域和序列定义的共轭低聚物可以通过沉淀或自动液相色谱法快速纯化。这些合成的离散低聚物可用于迭代指数和顺序生长，以获得线性和树枝状星型聚合物。此外，还可以通过缩合聚合方便地从这些离散低聚物制备不同拓扑序列可控的共轭聚合物。通过研究这些聚合物的结构-性能关系，我们发现光学性质强烈受到区域化学的影响，这可能为光电高分子材料的设计提供启示。
