Boran A, González-Gómez R, Hennessey S, Farràs P
School of Biological and Chemical Sciences, Ryan Institute, University of Galway H91 CF50 Galway Ireland
Chem Sci. 2025 Jun 24;16(27):12227-12241. doi: 10.1039/d5sc03670d. eCollection 2025 Jul 10.
Porous materials have many promising characteristics, including tuneable chemical and optical properties, modifiable porosities and large surface areas. Long-range order frameworks have effective evaluation methods as a result of their crystallinities and in this context, nanoscale analysis, namely single-crystal X-ray diffraction, is a particularly useful approach for optimising the structure-property relationships. Metal-covalent organic frameworks (MCOFs), synthesised by incorporating a metal complex into a stable covalent organic framework (COF) backbone, have shown considerable promise for a variety of applications. Nonetheless, their wide-scale implementation remains hindered due to difficulties in structurally mapping them; their typically reduced crystallinities result in major challenges for their structural determination. By classifying MCOFs as metalated COFs (MeCOFs) and metalloligand COFs (MLCOFs), the characterisation of these lower crystallinity frameworks can be carried out according to their distinctive architecture using a combination of complementary structural analysis techniques. This perspective highlights examples of a synergistic approach to the structural elucidation of MLCOFs to overcome obstacles related to their crystalline nature, generating an atomic map through a combination of nano and macroscale characterisation procedures supported by theoretical modelling tools. The effective use of structural characterisation methods is considered in this perspective, which can reveal key information regarding the structure-activity relationships as they relate to MLCOFs.
多孔材料具有许多有前景的特性，包括可调节的化学和光学性质、可改变的孔隙率以及大的表面积。由于其结晶度，长程有序框架有有效的评估方法，在这种情况下，纳米级分析，即单晶X射线衍射，是优化结构-性能关系的一种特别有用的方法。通过将金属配合物纳入稳定的共价有机框架（COF）主链中合成的金属-共价有机框架（MCOF），在各种应用中显示出了巨大的潜力。尽管如此，由于在构建其结构图谱方面存在困难，它们的大规模应用仍然受到阻碍；其通常降低的结晶度给它们的结构测定带来了重大挑战。通过将MCOF分类为金属化COF（MeCOF）和金属配体COF（MLCOF），可以使用互补结构分析技术的组合，根据这些较低结晶度框架的独特结构来进行表征。这一观点突出了一种协同方法的实例，用于阐明MLCOF的结构以克服与其晶体性质相关的障碍，通过由理论建模工具支持的纳米和宏观尺度表征程序的组合生成原子图谱。从这个角度考虑了结构表征方法的有效使用，这可以揭示与MLCOF相关的结构-活性关系的关键信息。
