Side-chain functionalized supramolecular helical brush copolymers
Side-chain functionalized supramolecular helical brush copolymers
复制标题
侧链功能化的超分子螺旋刷状共聚物
DOI：
10.1039/d1py00373a
复制
发表时间：
2021-06-02
影响因子：
4.6
通讯作者：
Weck, Marcus
中科院分区：
文献类型：
--
作者：
Deng, Ru;Wang, Chengyuan;Weck, Marcus
我们报道了通过金属催化的手性和非手性异氰酸酯单体的控制聚合，合成了具有烷氧基羰基侧链的多异氰酸酯无规共聚物(co-PIC)。吡啶官能化的非手性单体提供了功能位点，而手性单体驱动了单手优先螺旋的形成。H-1核磁共振和UV-Vis光谱表明，侧链功能化的螺旋聚合物与苍白的钳形配体发生了自组装。圆二色谱(CD)证实侧链的自组装不影响主链的螺旋度。我们通过将co-PIC主链与遥控螺旋聚苯乙烯S进行金属配位，合成了超分子螺旋刷状共聚物。H-1核磁共振和UV-Vis光谱证实了金属配位，CD测量表明主链保持了螺旋构象。此外，粘度计测量证实了高分子量聚合物的形成，而动态光散射证实了所得到的超分子刷状共聚物的流体动力学半径增加。我们的方法构建复杂的3D材料，具有完全合成的、包含构建块的二级结构。我们认为这是一个构建结构控制的高度复杂的3D超分子材料的平台。
We report poly(isocyanide)-based random copolymers (co-PIC) featuring alkoxycarbonyl-based side-chains synthesized via the metal-catalyzed controlled polymerization of chiral and achiral isocyanide monomers. The pyridine-functionalized achiral monomer provides functional sites while the chiral monomer drives the formation of a one-handed preferred helix. The side-chain functionalized helical polymer undergoes self-assembly with palladated pincer ligands, as evidenced by H-1 NMR and UV-Vis spectroscopies. Circular dichroism (CD) spectroscopy confirms that the side-chain self-assembly does not affect the backbone helicity. We construct supramolecular helical brush copolymers via the metal coordination of the co-PIC backbone with telechelic poly(styrene)s. H-1 NMR and UV-Vis spectroscopies confirm the metal coordination, and CD measurements suggest that the backbone retains its helical conformation. Additionally, viscometry measurements verify the formation of high molecular weight polymers while dynamic light scattering confirms the increasing hydrodynamic radii of the resulting supramolecular brush copolymers. Our methodology constructs complex 3D materials with fully synthetic, secondary structure containing building blocks. We view this as a platform for building architecturally controlled 3D supramolecular materials with high degrees of complexity.