阿佐比斯未探究的异构化途径 ((-15冠-5)):对蝶冠以太的计算研究
Dilawar Singh Sisodiya1, Sk Musharaf Ali2, Anjan Chattopadhyay1
1Department of Chemistry, Birla Institute of Technology and Science (BITS), Pilani, K.K. Birla Goa Campus, Zuarinagar 403726, India.
The journal of physical chemistry. A
|August 1, 2023
概括
计算研究揭示了光响应性阿佐比斯 (-15-皇冠-5) 的异构化途径. 跨同位素通过N=N拉伸放松,而cis同位素则无障碍同位素化,形成跨同位素.
科学领域:
- 摄影化学的使用.
- 计算化学计算化学
- 分子异构化分子异构化
背景情况:
- 光响应性亚素在分子开关和材料科学中至关重要.
- 了解阿佐比斯 ((-15-皇冠-5) 的异构化机制是设计高级功能材料的关键.
- 之前的研究已经探讨了亚博同质化,但需要对替代变体进行详细的计算洞察.
研究的目的:
- 通过计算来研究光响应性阿佐比斯的 trans → cis 和 cis → trans 异构化途径 (-15-皇冠-5).
- 阐明激发状态 (S2,S1) 和形交点在异构化过程中的作用.
- 为了将异构化通道与未被替代的亚博的异构化通道进行比较.
主要方法:
- 用密度函数理论 (DFT) 的计算来建模潜在能量表面.
- 进行了激发状态 (ππ*和nπ*) 和形交点 (S2/S1和S0/S1) 的分析.
- 对反应坐标的研究,包括N=N的拉伸,扭转和外平面运动.
主要成果:
- 变异构体的光刺激 (S2) 通过平面最小值和S2/S1沿N=N拉伸坐标的形交叉点导致放松.
- cis同位体的激发状态 (S1) 经历无障碍通道到S0/S1扭曲形交叉点,从而促进跨同位体的形成.
- 还确定了一种效率较低的协同逆转路径和通过逆转的热 cis → trans 异构化.
结论:
- 这项研究提供了详细的机理理解的阿扎比斯 (-15-皇冠-5) 光异构化.
- 与未被替代的亚博相比,异构化途径的关键差异得到了强调.
- 这些发现有助于合理设计光响应分子系统.
相关概念视频
Crown Ethers
5.3K
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...
5.3K
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
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
2.8K
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.
2.8K
Isomerism in Alkenes
12.0K
Alkenes like 1-butene and 2-butene exhibit constitutional isomerism, as they differ in the position of the double bond. Further, 2-butene exhibits stereoisomerism and exists as two distinct compounds differing in spatial arrangement.
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
12.0K
E1 Reaction: Stereochemistry and Regiochemistry
9.7K
One of the critical aspects of the E1 reaction mechanism, as also observed in E2, is the regiochemistry, with multiple regioisomers obtained as products. In the example discussed, the presence of water as a weak base favors elimination over substitution to generate two alkenes. Given that alkenes’ stability increases with the number of alkyl groups across the double bond, typically, E1 reactions lead to the Zaitsev product, for this is more substituted and stable than the Hofmann product.
9.7K
Stereoisomerism of Cyclic Compounds
9.0K
In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...
9.0K


