大学化学 >> 2021, Vol. 36 >> Issue (8): 2011027.doi: 10.3866/PKU.DXHX202011027

知识介绍 上一篇    下一篇

从溶剂笼到分子笼

李悦, 阮文娟()   

  • 收稿日期:2020-11-06 录用日期:2021-01-12 发布日期:2021-01-15
  • 通讯作者: 阮文娟 E-mail:wjruan@nankai.edu.cn
  • 作者简介:阮文娟, Email: wjruan@nankai.edu.cn
  • 基金资助:
    天津市物理化学系列课程教学团队建设项目;南开大学教育教学改革项目

From Solvent Cage to Molecular Cage

Yue Li, Wenjuan Ruan()   

  • Received:2020-11-06 Accepted:2021-01-12 Published:2021-01-15
  • Contact: Wenjuan Ruan E-mail:wjruan@nankai.edu.cn

摘要:

在物理化学中,对溶液中的反应通常用笼效应来描述溶剂与反应物质间的关系。一般认为,溶质(反应物质)是被溶剂分子所构成的笼包围;溶剂笼是柔性的,其大小、形状取决于溶质分子;反应物分子会在出入溶剂笼的过程中遭遇、碰撞、发生反应。随着合成技术的发展,人们合成出了以共价键、配位键连接的分子笼。相对于由范德华力所构筑的溶剂笼,分子笼表现出更高的刚性,因此其对化学反应可产生更为显著的影响。有别于传统催化剂的化学方式(与反应物、中间体等成键),当化学反应在分子笼中进行时,分子笼可通过富集反应物、改变反应物构型、影响中间产物的结构以及限制产物尺寸等一系列物理方式对反应的速率、选择性造成影响。该领域的研究对于深入揭示化学反应机理、调控所进行的反应均具有重要意义。

关键词: 溶剂笼, 分子笼, 化学反应, 结构刚性

Abstract:

In physical chemistry, the model of solvent cage is used to describe the relationship between reactant and solvent. In this model, the reactant molecule is surrounded by the cage constructed with solvent molecules. The solvent cage is flexible, and its size and shape are determined by the central reactant molecule. The encounter, collision and reaction between reactant molecules proceed in solvent cages. With the advancement of synthetic techniques, molecular cages, which are constructed by covalent and coordination bonds, are developed. Relative to the solvent cages connected with van der Waals force, molecular cages show much higher rigidity, thus, their effects on the reactions is expected to be more remarkable. Different from traditional catalysts that participate the reaction through the binding with reactants or intermediates, molecular cages could affect the reaction through a physical manner. By enriching reactants, altering the configuration of reactants, changing the structure of intermediates and limiting the growth of products, molecular cages could exert a profound influence on the rate and selectivity of the reaction. The research on this field is significant for the elucidation of reaction mechanism and the modulation of reaction proceeding.

Key words: Solvent cage, Molecular cage, Chemical reaction, Structural rigidity

MSC2000: 

  • G64