灯,开关,行动! 适应性自组系统中的几何光异构的影响
Marco Ovalle1, Charlotte N Stindt1, Ben L Feringa1
1Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 3, Groningen 9747 AG, The Netherlands.
Journal of the American Chemical Society
|November 5, 2024
概括
研究人员开发了光控制的动态纳米结构, 这一突破使得复杂的物质和类似生命的物质能够被精确地控制,为新的分子机器铺平了道路.
科学领域:
- 超分子化学
- 材料科学
- 化学工程
背景情况:
- 自然动态纳米结构表现出环境适应性,这是先进化学系统所追求的特征.
- 设计这种适应性系统是复杂的,通常会产生不可预测的混合物和具有挑战性的特征.
研究的目的:
- 开发用于动态纳米结构组装的光控制系统.
- 使用可光切换的构件实现不同架构之间的可预测和可逆适应.
主要方法:
- 使用内在的可光切换构建块来控制自组装架构.
- 基于互补单元存在的和宏循环结构之间的可逆转换.
- 展示了七个不同的光诱导的变化.
主要成果:
- 使用光实现了前所未有的纳米结构形成控制和多样化.
- 在子和宏循环架构之间可逆调整,访问更高能量的组件.
- 展示了自己选择的补充单位来决定主导的架构.
结论:
- 开发的可光切换系统为设计适应性化学系统提供了一种新的策略.
- 这些发现使得随需的消散性宏循环和短暂的纳米结构,如网状和聚合物材料.
- 未来的工作可以通过调整互补单元来探索各种短暂的纳米结构.
相关概念视频
Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.8K
Stereoisomerism
11.8K
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...
11.8K
Thermal and Photochemical Electrocyclic Reactions: Overview
2.3K
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.
2.3K
Woodward–Hoffmann Selection Rules and Microscopic Reversibility
3.0K
Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
3.0K
Thermal Electrocyclic Reactions: Stereochemistry
2.0K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.0K
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.0K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.0K


