在光色的dithienylcyclopentenes 中的电色化
1Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC, Canada V5A 1S6.
Journal of the American Chemical Society
|March 20, 2003
概括
开发了新的光色和电色化合物. 这些1,2-bis(3-thienyl) cyclopentene衍生物通过光或电化学氧化在无色和有色状态之间切换.
科学领域:
- 材料科学 材料科学 材料科学
- 有机化学 有机化学
- 摄影化学的使用.
背景情况:
- 光色材料在暴露于光线时会改变颜色.
- 电色材料在受到电刺激时会改变颜色.
- 环烯衍生物提供可调节的电子特性.
研究的目的:
- 为了合成和表征新的1,2-bis(3-thienyl) cyclopentene衍生物.
- 为了研究这些化合物的光色和电色行为.
- 探索它们在响应性材料中的潜在应用.
主要方法:
- 烯和烯替代1,2-bis(3-烯) cyclopentene 的合成.
- 紫外线-Vis光谱法用于监测光色过渡.
- 电化学方法研究电色特性.
主要成果:
- 化合物表现出可逆光色,在紫外线/可见光下在无色 (开环) 和有色 (闭环) 状态之间切换.
- 在这些衍生品中观察到前所未有的电色.
- 催化氧化可以使环闭状态转化为环开状态.
结论:
- 研究的1,2-bis(3-thienyl) cyclopentene衍生物具有光色和电色两种特性.
- 这些材料通过光或电化学刺激提供可调色的颜色变化.
- 智能窗口,显示器和光学数据存储中的应用潜力.
相关概念视频
Colors and Magnetism
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
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
Diels–Alder Reaction: Characteristics of Dienes
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Aromatic Hydrocarbon Cations: Structural Overview
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Removing one hydrogen from the intervening CH2 group with both...


