一个蝶冠以太的双复合物作为一个可光调的超分子催化剂
Roberta Cacciapaglia1, Stefano Di Stefano, Luigi Mandolini
1Dipartimento di Chimica and ICCOM CNR-Sezione di Roma, Università La Sapienza, Box 34-ROMA 62, 00185 Roma, Italy. roberta.cacciapaglia@uniroma1.it
Journal of the American Chemical Society
|February 20, 2003
概括
一个双复合物的催化效率是可逆控制使用光. 催化剂是一种催化剂.
科学领域:
- 超分子化学 超分子化学
- 催化剂是一种催化剂.
- 摄影化学的使用.
背景情况:
- 阿佐二衍生物以其光异构化特性而闻名.
- 皇冠乙烯可以与金属离子形成复合物,影响催化活性.
- 通过光等外部刺激来控制催化过程是化学的一个关键目标.
研究的目的:
- 开发一种催化剂,其效率可以通过光可逆调节.
- 为了研究光诱导催化活性调节的机制.
- 为了实现催化过程的持续光调节.
主要方法:
- 合成一个含有阿佐本单元的双复合物.
- 用光化学辐射诱导阿佐烯部分的 cis-trans 异体化.
- 监测化衍生物的基本乙醇化中的催化活性.
- 改变激发波长和辐射时间以控制催化剂活动.
主要成果:
- 在"高"和"低"状态之间实现了可逆的催化效率切换.
- 催化剂的cis同位素与基质形成了一个更具生产力的复合体.
- 证明了在中间水平上对催化活性的持续光调节.
- 光静态状态之间的快速相互转换允许在单个实验中重复切换.
结论:
- 双亚博复合体作为一个可光切换的催化剂.
- 对催化效率的光化学控制是可行的和可调的.
- 这项工作为开发光敏催化系统提供了一条途径.
相关概念视频
Crown Ethers
Crown ethers are cyclic polyethers that contain multiple oxygen atoms, usually arranged in a regular pattern. The first crown ether was synthesized by Charles Pederson while working at DuPont in 1967. For this work, Pedersen was co-awarded the 1987 Nobel Prize in Chemistry. Crown ethers are named using the formula x-crown-y, where x is the total number of atoms in the ring and y is the number of ether oxygen atoms. The term 'crown' refers to the crown-like shape that these ether molecules take.
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.
Thermal Electrocyclic Reactions: Stereochemistry
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.
Photochemical Electrocyclic Reactions: Stereochemistry
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
Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
Birch reduction uses solvated electrons as reducing agents. The reaction converts benzene to 1,4-cyclohexadiene. The reaction proceeds by the transfer of a single electron to the ring to form a benzene radical anion. This anion is highly basic—it abstracts a proton from the alcohol to form a cyclohexadienyl radical. Another single electron transfer gives the cyclohexadienyl anion. A proton transfer from the alcohol forms 1,4-cyclohexadiene. Since this reduction occurs via radical anion...
Cycloaddition Reactions: MO Requirements for Photochemical Activation
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.


