Ge Yanqing, Huang Shaofeng, Yuan Zhehao, Zhang Wei
School of Chemistry and Pharmaceutical Engineering, Shandong First Medical University & Shandong Academy of Medical Sciences, Taian 271016, China.
Department of Chemistry, University of Colorado Boulder, Boulder, Colorado 80309, United States.
Acc Chem Res. 2025 Aug 18. doi: 10.1021/acs.accounts.5c00393.
ConspectusCrystalline porous frameworks, such as covalent organic frameworks (COFs), metal-organic frameworks (MOFs), and hydrogen-bonded organic frameworks (HOFs), have demonstrated exceptional potential in diverse applications, including gas adsorption/separation, catalysis, sensing, electronic devices, etc. However, the building blocks for constructing ordered frameworks are typically limited to multisubstituted aromatic small molecules, and uncontrolled interpenetration has remained a long-standing challenge in the field. Shape-persistent macrocycles and molecular cages have garnered significant attention in supramolecular chemistry and materials science due to their unique structures and novel properties. Using such preporous shape-persistent 2D macrocycles or 3D cages as building blocks to construct extended networks is particularly appealing. This hierarchical assembly approach not only mitigates the issue of interpenetration but also enables the integration of diverse properties in an emergent fashion. Since our demonstration of the first organic cage framework (OCF) in 2011 and the first macrocycle-based ionic COFs (ICOFs) in 2015, substantial advancements have been made over the past decade. In this Account, we will summarize our contributions to the development of crystalline porous frameworks, consisting of shape-persistent macrocycles and molecular cages as preporous building blocks, via hierarchical dynamic covalent assembly. We will begin by reviewing representative design strategies and the synthesis of shape-persistent macrocycles and molecular cages from small molecule-based primary building blocks, emphasizing the critical role of dynamic covalent chemistry (DCvC). Next, we will discuss the further assembly of preporous macrocycle/cage-based secondary building blocks into extended frameworks, followed by an overview of their properties and applications. Finally, we will highlight the current challenges and future directions for this hierarchical assembly approach in the synthesis of crystalline porous frameworks. This Account offers valuable insights into the design and synthesis of functional porous frameworks, contributing to the advancement of this important field.
综述
晶体多孔框架，如共价有机框架（COF）、金属有机框架（MOF）和氢键有机框架（HOF），在包括气体吸附/分离、催化、传感、电子器件等在内的各种应用中展现出了卓越的潜力。然而，构建有序框架的基本单元通常局限于多取代芳香小分子，并且不受控制的相互贯穿一直是该领域长期存在的挑战。形状持久的大环和分子笼因其独特的结构和新颖的性质，在超分子化学和材料科学中受到了广泛关注。使用这种预多孔的形状持久二维大环或三维笼作为基本单元来构建扩展网络尤其具有吸引力。这种分级组装方法不仅减轻了相互贯穿的问题，还能够以一种涌现的方式整合多种性质。自2011年我们首次展示有机笼框架（OCF）以及2015年首次展示基于大环的离子共价有机框架（ICOF）以来，在过去十年中取得了重大进展。在这篇综述中，我们将总结我们通过分级动态共价组装对由形状持久的大环和分子笼作为预多孔基本单元组成的晶体多孔框架发展所做出的贡献。我们将首先回顾代表性的设计策略以及从小分子基元构建形状持久的大环和分子笼的合成方法，强调动态共价化学（DCvC）的关键作用。接下来，我们将讨论基于预多孔大环/笼的二级构建单元进一步组装成扩展框架的过程，随后概述它们的性质和应用。最后，我们将突出这种分级组装方法在晶体多孔框架合成中当前面临的挑战和未来方向。这篇综述为功能性多孔框架的设计和合成提供了有价值的见解，有助于推动这一重要领域的发展。
