分子"指南针"和"陀螺镜". I. 一个开放旋转机与一个 bis ((triarylmethyl) 框架的恰当合成和固态动力学
Zaira Dominguez1, Hung Dang, M Jane Strouse
1Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095-1569, USA.
Journal of the American Chemical Society
|March 14, 2002
概括
研究人员使用两步过程合成了新的分子指南针和陀螺仪. 这些分子表现出独特的旋转动力学,在分子机械和先进材料中具有潜在的应用.
科学领域:
- 分子工程是分子工程.
- 超分子化学 超分子化学
- 材料科学是一种材料科学.
背景情况:
- 设计具有特定拓性质的分子对于开发先进的功能材料至关重要.
- 宏观指南针和陀螺仪依赖于旋转力学,启发了分子水平的类似物.
研究的目的:
- 合成和描述具有类似于宏观指南针和陀螺仪的拓学的分子.
- 研究这些新型分子结构的旋转动力学和热稳定性.
主要方法:
- 通过两步过程合成1,4-bis(3,3,3-triphenylpropynyl) .
- 使用单晶X射线衍射和可变温度固态核磁共振 (NMR) 的结构特征.
- 使用差分扫描热度计 (DSC) 和热重力计分析 (TGA) 进行热稳定性评估.
主要成果:
- 目标分子的成功制备,其中中央烯充当陀螺仪轮子,三烯基组充当轴/屏蔽.
- 类酸盐晶体结构及其解溶形式的表征.
- 对烯基组的旋转动态进行双重翻转过程的识别.
- 固态旋转障碍的估计:在克拉酸盐中约12.8 kcal/mol,在脱样本中约14.6 kcal/mol.
结论:
- 合成的分子在分子层面上有效地模仿了宏观陀螺仪拓.
- 这些分子陀螺仪的旋转动力学和稳定性已经得到量化.
- 这项工作为设计具有可控旋转运动的分子机器提供了基础.
相关概念视频
Newman Projections
Different notations are used to represent the three-dimensional structure of molecules on two-dimensional surfaces. One of the most commonly used representations is the dash-wedge formula. The dashed wedges, solid wedges, and the plane lines indicate the groups situated behind the plane, coming out of the plane, and in the plane, respectively.
The organic molecules rotate across the single bonds leading to numerous temporary three-dimensional structures of varying energy known as conformers.
The organic molecules rotate across the single bonds leading to numerous temporary three-dimensional structures of varying energy known as conformers.
Chirality
Chirality is a term that describes the lack of mirror symmetry in an object. In other words, chiral objects cannot be superposed on their mirror images. For example, our feet are chiral, as the mirror image of the left foot, the right foot, cannot be superposed on the left foot.
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
Molecules with Multiple Chiral Centers
Molecules that possess multiple chiral centers can afford a large number of stereoisomers. For instance, while some molecules like 2-butanol have one chiral center, defined as a tetrahedral carbon atom with four different substituents attached, several molecules like butane-2,3-diol have multiple chiral centers. A simple formula to predict the number of stereoisomers possible for a molecule with n chiral centers is 2n. However, there can be a lower number where some of the stereoisomers are...
Fischer Projections
Learning to draw Fischer projections of molecules and understanding their relevance plays a crucial role in the visual depiction of organic molecules. A Fischer projection is a two-dimensional projection on a planar surface to simplify the three-dimensional wedge–dash representation of molecules. This is especially helpful in the case of molecules with multiple chiral centers that can be difficult to draw. Here, all the bonds of interest are represented as horizontal or vertical lines. While...
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
Machines
Machines are complex structures consisting of movable, pin-connected multi-force members that work together to transmit forces. One example of a machine is the cutting plier, which is used to cut wires by applying forces to its handles. When equal and opposite forces are exerted on the handles of the cutting plier, they cause the cutting edges to come together and apply equal and opposite reaction forces on the wire, which are greater than the applied forces.
A free-body diagram of the...
A free-body diagram of the...


