迪 ((p-dibenzi) [40]decaphyrin ((1.0.0.0.0.1.0.0.0.0) PdII 复合物:一个微弱的Hückel 38π-芳香宏循环
Chengwei Wang1, Ling Xu1, Yutao Rao1
1Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Educational of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, China.
Chemistry, an Asian journal
|November 20, 2023
概括
合成了具有莫比乌斯拓的新宏循环. 复合物表现出芳香性,与其非芳香BF2对应物不同,表现出独特的结构和电子特性.
科学领域:
- 超分子化学 超分子化学
- 有机合成 有机合成
- 计算化学计算化学
背景情况:
- 四烯醇宏循环在各种化学和生物过程中具有基本作用.
- 探索新的宏观循环架构对于推进材料科学至关重要.
- 宏观循环中的Möbius拓具有独特的电子和结构特征.
研究的目的:
- 合成新的二甲 (p-) [40]甲氨酸和三甲 (p-) [60]五甲氨酸BF2复合物.
- 研究这些宏观循环及其金属复合物的结构和电子特性.
- 确定合成化合物的芳香度和拓特征.
主要方法:
- 对于宏观循环合成的苏苏基-米亚乌拉合反应.
- 将BF2复合物转化为自由基,然后转化为PdII复合物.
- 用光谱 (UV-Vis) 和电化学 (循环电压测量) 分析来描述电子属性.
主要成果:
- 成功合成了Di(p-基) [40]甲氨酸BF2和tris(p-基) [60]五甲氨酸BF2复合体.
- 这两种BF2复合体都表现出Möbius拓,但由于被破坏的结合,它们是非芳香的.
- 该bis-PdII复合体显示弱的Hückel 38π-aromaticity,具有明显的光谱特征和一个小的HOMO-LUMO间隙.
- 该bis-PdII复合体采用一个八号形状,其中有一个化和一个基单元.
结论:
- 纳入p-烯单元影响了四聚烯宏循环的芳香度和拓.
- 金属化 (PdII) 可以在其他非芳香的莫比乌斯宏观循环中诱导芳香性.
- 这项研究揭示了复杂的宏观循环系统中拓,芳香度和分子构成之间的独特相互作用.
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