一个终端二乙烯的单晶到单晶的拓化学聚合物:两个显著的转换产生了相同的合聚合物
Xi Ouyang1, Frank W Fowler, Joseph W Lauher
1Department of Chemistry, State University of New York, Stony Brook, New York 11794-3400, USA.
Journal of the American Chemical Society
|October 9, 2003
概括
主客化学使得三螺旋共晶的产生成为可能,导致终端二乙烯的第一个结构特征聚合,并显著增加了晶体密度.
科学领域:
- 超分子化学 超分子化学
- 晶体工程 晶体工程
- 聚合物化学 聚合物化学
背景情况:
- 主机-客人化学提供了对分子组装的精确控制.
- 终端二乙烯是用于聚合的多功能单体.
- 结构性特征是理解反应机制的关键.
研究的目的:
- 为了准备和结构性地表征二氧化二氧化宿主和源醇衍生的终端二乙烯的共晶体.
- 为了研究这些共晶体内对齐的二乙烯功能的聚合.
- 分析聚合过程中的结构变化,并比较不同的聚合途径.
主要方法:
- 宿主-客人复合形成共晶体.
- 用X射线结晶学测定共晶和聚合物的结构.
- 用热分析来诱导聚合.
主要成果:
- 一个三螺旋共晶结构是由对齐的二乙烯单元形成的.
- 在加热后发生聚合,产生相应的聚合物.
- 一种晶体水合物也显示出适当的二乙烯对齐,并在50°C时聚合.
- C1碳的前所未有的2.4 Å向内摆动导致晶体密度增加了9%.
- 这代表了终端二甲基乙烯的第一个结构特征聚合.
结论:
- 宿主-客人化学提供了一条精确控制二乙烯聚合的途径.
- 观察到的聚合机制,包括显著的C1运动和密度增加,提供了新的见解.
- 这些发现为通过控制的固态聚合物设计具有定制性质的新材料铺平了道路.
相关概念视频
Stereoisomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
Polymer Classification: Crystallinity
Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.


