在聚合诱导的分子转子中的激发状态芳香相互作用
Jiri Sturala1, Marc K Etherington1, Aisha N Bismillah1
1Department of Chemistry and ‡Department of Physics, Durham University , Lower Mountjoy, Stockton Road, Durham DH1 3LE, United Kingdom.
Journal of the American Chemical Society
|November 21, 2017
概括
光体中的环可以形成穿越空间的芳香二次体状态,影响光. 这种意想不到的现象影响了发光探测器和光电子设备的设计.
科学领域:
- 摄影化学
- 材料科学
- 有机化学
背景情况:
- 芳香基如环在光体中用于阻碍旋转和改善固态发光.
- 这些芳香基通常不被认为参与影响光的透空间相互作用.
研究的目的:
- 研究具有不同数量的基环分子旋转器的光发光特性.
- 在这些分子旋转器的光发射中探索穿越空间相互作用的作用.
主要方法:
- 用3,5,6和7的环分子旋转器的合成和表征.
- 光发光光谱分析溶液和固态的辐射特性.
- 计算模型以了解激发状态的形成.
主要成果:
- 两个环旋转器表现出源于穿越空间的芳香二次元状态的光,而不是局部激发状态.
- 这些二聚体状态在各种环境中通过内部或分子间相互作用形成,包括聚合诱导的排放条件.
- 计算模型支持了芳香二元激发状态在观察到的光物理性质中的作用.
结论:
- 透过空间的芳香二聚体状态是环分子旋转器光发光的重要因素.
- 在设计光探针和光电子装置时应考虑这种现象.
- 这些发现表明适用于含有芳香成分的光原体的一般原则.
相关概念视频
π Electron Effects on Chemical Shift: Aromatic and Antiaromatic Compounds
1.9K
In aromatic compounds, such as benzene, the circulation of (4n + 2) π-electrons sets up a diamagnetic or diatropic ring current around the perimeter of the molecule. This current induces a magnetic field that opposes the external field inside the ring and reinforces it on the outside. The protons in benzene are deshielded and exhibit high chemical shifts in the range 6.5–8.5 ppm. The shielding effect at the center of the ring is evident in complex aromatic molecules, such as...
1.9K
Photochemical Electrocyclic Reactions: Stereochemistry
2.3K
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
2.3K
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.8K
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.
2.8K
Molecular Spectroscopy: Absorption and Emission
4.8K
Molecules possess discrete energy levels called quantum states. Unlike atoms, which have simpler energy levels, molecules possess additional rotational and vibrational energy levels. Each energy level is separated by an energy gap, with the gaps between adjacent electronic, vibrational, and rotational levels varying significantly. The three types of energy levels in a diatomic molecule are shown in Figure 1.
4.8K
Variables Affecting Phosphorescence and Fluorescence
1.5K
Fluorescence and phosphorescence are essential phenomena in fields like analytical chemistry, biological imaging, and materials science, where they detect molecular properties and visualize cellular structures. Understanding the variables that influence these luminescent behaviors is crucial for maximizing accuracy and efficiency in their applications. These variables can broadly be grouped into chemical structure, solvent properties, and external conditions, each playing a distinct role in...
1.5K
Thermal and Photochemical Electrocyclic Reactions: Overview
3.1K
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.
3.1K


