一个新型的功能化特皮里迪尔连接体作为光敏超分子架构的构建块. 合成,结构和电子表征
Philippe Lainé1, Fethi Bedioui, Philippe Ochsenbein
1Laboratoire de Chimie Physique, CNRS UMR 8000, Université Paris-Sud, Bâtiment 350, 91405 Orsay Cedex, France.
Journal of the American Chemical Society
|February 14, 2002
概括
合成了新的光敏感分子,其中含有被电子受体替代的特皮里迪尔配体. 这些刚性棒超分子架构显示了长距离光诱导电子转移的潜力,在溶液中观察到持久的伪垂直形状.
科学领域:
- 超分子化学 超分子化学
- 摄影化学的使用.
- 材料科学 材料科学 材料科学
背景情况:
- 新型光敏感分子的开发对于太阳能转化等先进应用至关重要.
- 电子受体 (A) 和电子捐赠体 (D) 替代联体是设计功能性超分子系统的关键组成部分.
- 了解光活性分子中的结构-性质关系指导了高效电子转移系统的设计.
研究的目的:
- 设计和合成一种新的类型的电子受体替代特皮里迪尔连接物及其金属复合物.
- 为光诱导电子转移研究构建纳米尺度的刚性棒状光敏化超分子架构.
- 研究这些新型超分子系统的结构特征和电子特性.
主要方法:
- 合成三烯二烯衍生型二烯联体及其 (II) 和 (II) 复合物.
- 合体和金属复合物的单晶X射线衍射分析.
- 溶液1HNMR光谱,包括ROESY实验,用于研究分子构成和相互作用.
主要成果:
- 成功合成了新型电子受体替代特皮里基联体 (H(3)TP(+) -tpy,H(3)TP(+) -ptpy) 和它们的M(tpy) ((2)(2+) 和M(ptpy) ((2)(2+) 复合体 (P0,P1).
- 形成包含电子捐赠体连接体的超分子结构 (多聚),形成刚性棒状结构.
- 在固态和溶液中,证明了接受器和光敏剂子单元之间的持久的伪垂直形状.
结论:
- 设计的超分子架构显示了长距离光诱导电子转移应用的潜力.
- 伪垂直形状在流体介质中保持,这表明子单位之间的电子通信有限.
- 获得了对D-A系统中组件间合的替代效应和结合的洞察.
相关概念视频
Photochemical Electrocyclic Reactions: Stereochemistry
2.2K
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
2.2K
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.6K
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.
2.6K
Thermal and Photochemical Electrocyclic Reactions: Overview
2.9K
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.
2.9K


