自组装的共价连接波状链的表面合成与选址的合规切换
Limei Wang1, Rui Zhu2, Zhitao Shen1
1Key Laboratory for Quantum Matter Science, Key Laboratory of Photovoltaic Materials, Henan University, Kaifeng 475004, China.
Journal of the American Chemical Society
|January 12, 2023
概括
研究人员在银面上制造出有序的波形聚合物链, 这种在表面合成的突破利用了对受控结构的特定化学反应和相互作用.
科学领域:
- 表面科学
- 聚合物化学
- 超分子化学
背景情况:
- 在表面上的聚合物构造决定了形状和特性.
- 形态多样性往往与表面合成中的无序结构有关.
研究的目的:
- 研究从形状灵活的前体的有序结构的表面合成.
- 在自组合的聚合物链中展示选择性结构切换.
主要方法:
- 聚合物链的共价连接的乌尔曼反应.
- 高分辨率扫描道显微镜 (STM) 用于分子级观测.
- 密度函数理论 (DFT) 计算用于机制分析.
主要成果:
- 在Ag111上合成了两个不同的,有序的,共价连接的波状聚合物链.
- 链表现出特定位置的形状切换与独特的重复单元安排.
- 确定Br·H·C相互作用和Ag{111) 基质对于有序结构的形成至关重要.
结论:
- 表面合成甚至可以从形状灵活的前体中产生有序结构.
- 特定的分子间相互作用和基质效应是控制聚合物组装的关键.
- 这项工作扩大了表面反应的范围,用于创建复杂的分子结构.
相关概念视频
Ziegler–Natta Chain-Growth Polymerization: Overview
3.4K
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
3.4K
Cationic Chain-Growth Polymerization: Mechanism
2.4K
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
2.4K
Anionic Chain-Growth Polymerization: Mechanism
2.1K
The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
2.1K
Anionic Chain-Growth Polymerization: Overview
2.1K
The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
2.1K
Radical Chain-Growth Polymerization: Chain Branching
2.0K
The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
2.0K
Radical Chain-Growth Polymerization: Mechanism
2.6K
The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this...
2.6K


