振动圆形二重化研究光学纯净的加密-A
Thierry Brotin1, Dominique Cavagnat, Jean-Pierre Dutasta
1Laboratoire de Chimie de l'ENS-LYON (UMR 5182-CNRS), Ecole Normale Supérieure de Lyon, 46 Allée d'Italie, 69364 Lyon 07, France.
Journal of the American Chemical Society
|April 20, 2006
概括
振动循环二元化 (VCD) 和密度函数理论 (DFT) 确定了加密-A.A.的绝对配置. 这项研究证明了VCD.
科学领域:
- 频谱学是一种光谱学.
- 计算化学的计算化学
- 分子结构的确定分子结构的确定
背景情况:
- 克里普托芬-A是一种大型的球形分子,没有奇拉中心.
- 确定大分子的绝对配置是一个挑战.
- 振动循环二元化 (VCD) 是阐明分子性的一种强大技术.
研究的目的:
- 为了确定光学纯净的加密-A.A.的绝对配置.
- 评估VCD对大,非性中心分子的适用性.
- 研究加密-A及其复合物的构造偏好.
主要方法:
- 在溶液中进行振动圆形二元体 (VCD) 测量.
- 密度函数理论 (DFT) 的计算 (B3PW91/6-31G级).
- 红外 (IR) 光谱用于光谱相关性.
主要成果:
- 通过使用VCD成功确定了cryptophane-A的绝对配置.
- 异构体的VCD光谱接近镜像,证实了性.
- DFT的计算显示出与实验性VCD和IR频谱的良好一致.
- 鉴定出了烯-烯-A复合体中的异形链接体的偏好抗构成.
- 在不同的溶剂中,以及空的和封闭的加密-A.中,形状仍然相似.
结论:
- VCD是有效的确定大分子的绝对配置,即使没有传统的奇拉中心.
- 这项研究证实了DFT计算在解释复杂VCD光谱中的有用性.
- 克里普托芬-A在其异形链接器中表现出稳定的抗构成,无论溶剂或客体存在.
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