Forgan Ross S
WestCHEM School of Chemistry, University of Glasgow Glasgow UK
Chem Sci. 2020 Apr 6;11(18):4546-4562. doi: 10.1039/d0sc01356k.
Exercising fine control over the synthesis of metal-organic frameworks (MOFs) is key to ensuring reproducibility of physical properties such as crystallinity, particle size, morphology, porosity, defectivity, and surface chemistry. The principle of modulated self-assembly - incorporation of modulator molecules into synthetic mixtures - has emerged as the primary means to this end. This perspective article will detail the development of modulated synthesis, focusing primarily on coordination modulation, from a technique initially intended to cap the growth of MOF crystals to one that is now used regularly to enhance crystallinity, control particle size, induce defectivity and select specific phases. The various mechanistic driving forces will be discussed, as well as the influence of modulation on physical properties and how this can facilitate potential applications. Modulation is also increasingly being used to exert kinetic control over self-assembly; examples of phase selection and the development of new protocols to induce this will be provided. Finally, the application of modulated self-assembly to alternative materials will be discussed, and future perspectives on the area given.
对金属有机框架（MOF）的合成进行精细控制是确保诸如结晶度、粒径、形态、孔隙率、缺陷率和表面化学等物理性质可重复性的关键。调制自组装原理——将调制分子引入合成混合物中——已成为实现这一目标的主要手段。这篇观点文章将详细介绍调制合成的发展，主要聚焦于配位调制，从最初旨在抑制MOF晶体生长的技术发展到如今经常用于提高结晶度、控制粒径、引入缺陷和选择特定晶相的技术。将讨论各种机械驱动力，以及调制对物理性质的影响以及这如何促进潜在应用。调制也越来越多地用于对自组装进行动力学控制；将提供相选择的例子以及诱导相选择的新方案的发展情况。最后，将讨论调制自组装在替代材料中的应用，并给出该领域的未来展望。
