不和 thiacrown 以太:合成,物理性质,和银复合物的形成
T Tsuchiya1, T Shimizu, N Kamigata
1Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University Minami-ohsawa, Hachioji, Tokyo 192-0397, Japan.
Journal of the American Chemical Society
|November 22, 2001
概括
合成和表征了新的不和 thiacrown 乙烯. 较大的戒指尺寸表现出更大的空洞和更容易的氧化,在金属复合中具有潜在的应用.
科学领域:
- 超分子化学 超分子化学
- 有机合成 有机合成
- 晶体工程公司 晶体工程
背景情况:
- 铁冠乙烯是含有硫原子的循环化合物,以其复杂化金属离子的能力而闻名.
- 与和的类型相比,不和的冠乙烯具有独特的结构和电子特性.
- 新型宏环化合物的合成和表征对于推进材料科学至关重要.
研究的目的:
- 合成一系列不同环形大小的不和 thiacrown 乙烯.
- 研究这些新型化合物的结构,光谱和电化学特性.
- 探索这些 thiacrown 以太与金属离子的复合行为.
主要方法:
- 通过cis-1,2-dichloroethylene与硫化的反应合成不和的 thiacrown 乙烯.
- 使用X射线结晶学对化合物4-8的结构确定.
- 通过UV-Vis光谱学和循环电压测量进行表征.
- 用银三酸进行复杂化研究.
主要成果:
- 成功合成了8种不和的冠乙烯 (1-8),环大小从6到27个成员.
- X射线晶体学揭示了更大的 thiacrown 乙烯 (5-8) 中的内牙硫原子协调,其腔体大小高达 5.36 Å.
- 紫外线-Vis光谱显示了取决于溶剂的吸收最大值,表明电子相互作用.
- 电化学研究表明,较大的不和 thiacrown 乙烯比较小的和它们的和类似物更容易氧化.
- 形成了一个银(I) 复合体 (9),其中五个硫原子中有三个与银离子协调.
结论:
- 这项研究成功地合成和表征了一系列新型的不和 thiacrown 乙烯.
- 结构性和电化学性质与戒指大小相关,突出调节性特征.
- 这些化合物显示出具有选择性金属离子结合的潜力,如银复合体形成所示.
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