通过将循环碳受体的尺寸从C18改为C16来促进电子转移
O A Stasyuk1, A A Voityuk1, A J Stasyuk1,2,3,4
1Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, C/ Maria Aurèlia, Capmany 69, 17003, Girona, Catalonia, Spain.
Chemistry (Weinheim an der Bergstrasse, Germany)
|March 26, 2024
概括
像C16和C18这样的循环碳分子表现出强大的电子吸收特性. 它们的复合物促进了快速的光诱导电子转移,由于更低的重组能量,C16加速了反应.
科学领域:
- * 超分子化学和材料科学.
- *计算化学和理论物理.
背景情况:
- *近期的合成进步使得新型循环碳分子的创造成为可能.
- * 表面化学和尖端诱导反应是关键的形成方法.
- * 循环碳正在探索它们独特的电子性质.
研究的目的:
- *以计算方式研究C16和C18环碳的电子性质.
- * 用于分析循环碳化合物的范德瓦尔斯 (vdW) 复合体与供体和受体分子.
- * 了解这些系统中光诱导电子转移 (ET) 的动态.
主要方法:
- *密度函数理论 (DFT) 的计算.
- * 范德瓦尔斯相互作用和复杂形成的分析.
- * 计算重组能量和电子转移速率.
主要成果:
- * 循环碳分子具有显著的电子吸收能力.
- * vdW复合体显示了热力学上有利的光诱导电子从捐赠体转移到循环碳.
- *电子转移发生在皮秒时间尺度上.
- * 由于重组能量较低,C16的ET反应比C18更快.
结论:
- * 循环碳是电子受体材料的有希望的候选物.
- *电子转移动态高度依赖于分子结构和性质.
- * C16和C18显示出在分子电子和光催化学中的应用潜力.
相关概念视频
Cycloaddition Reactions: Overview
2.6K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
2.6K
Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
2.2K
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...
2.2K
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
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
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.1K
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.
2.1K
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
2.7K
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.
2.7K


