过渡金属硫化物和相关复合物的光触发异构的未来前景
Sebastian B Vittardi1, Rajani Thapa Magar1, Douglas J Breen1
1Department of Chemistry and Chemical Biology, 300 Terrace Street NE, University of New Mexico, Albuquerque, New Mexico 87131-001 United States.
Journal of the American Chemical Society
|January 5, 2021
概括
光激活的光色分子,特别是和硫化复合物,经历有效的异构化. 这项研究探讨了它们的设计和过渡金属化学的未来方向.
科学领域:
- 无机化学
- 摄影化学
- 材料科学
背景情况:
- 光色分子表现出光激活的可比性质.
- 过渡金属上的硫氧化可以经历异构.
- 和聚胺复合物是研究得很好的光活性系统.
研究的目的:
- 突出和硫化复合物的设计标准.
- 阐明光触发硫化物异构化的机制.
- 探索光激活异构化的未来研究.
主要方法:
- 和硫化复合物的合成.
- 诱导和表征异构的光化学研究.
- 用光谱分析来确定结构变化.
主要成果:
- 证明了硫化配体的有效和高效的光触发异构.
- 确定了从S键到O键的激发状态异构化是关键机制.
- 提供了成功异构化的具体例子.
结论:
- 和硫化复合物是有前途的光色材料.
- 了解异构化机制对于设计新的光激活系统至关重要.
- 未来的工作将集中在用于增强异构的新型合成策略和配体设计上.
相关概念视频
Photochemical Electrocyclic Reactions: Stereochemistry
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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
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Thermal and Photochemical Electrocyclic Reactions: Overview
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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.
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Cycloaddition Reactions: MO Requirements for Photochemical Activation
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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.
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Preparation and Reactions of Sulfides
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Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
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Preparation and Reactions of Thiols
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Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
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Stereoisomerism
13.2K
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...
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