Carboxylate-Based Metal-Organic Framework and Coordination Polymer Glasses: Progress and Perspectives

Abstract

Conspectus: Coordination polymers (CPs) and metal-organic frameworks (MOFs) represent versatile materials with diverse structural and functional properties, making them appealing for various applications. However, their conventional forms, which are typically synthesized as powders or crystals, pose challenges due to limited processability and mechanical fragility. Recently, CP/MOF glasses have emerged as promising alternatives, offering enhanced processability while retaining some of the unique characteristics shown in the mother crystalline materials. Despite the prevalence of carboxylate ligands in CP/MOF synthesis, the development of carboxylate-based CP/MOF glasses has been limited compared to that of zeolitic-imidazole framework (ZIF)-based glasses. This is attributed to the strong metal-ligand bonds and low thermal stability of carboxylic acids, which hinder their melting in CP/MOF structures. Nonetheless, recent advancements have led to a surge in methods for synthesizing carboxylate-based CP/MOF glasses. So far, desolvation and melt-quenching have been introduced for achieving glass structures from CP/MOF precursors. The first melt-quenched MOF glass was reported in 2015 with ZIFs. However, we informally observed the melting of the MOF during thermal decomposition research of aliphatic carboxylate-based MOFs as a sacrificial template dating back to 2013. In that study, aliphatic ligands, instead of aromatic carboxylate, were employed due to their high lability, lower thermal stability, and high degree of freedom, which facilitated pyrolysis. The results were published with a focus on synthesizing hierarchically porous MgO via the pyrolysis of an aliphatic ligand-based Mg-MOF in an inert environment. A decade later, it was revisited and studied as the first melt-quenched carboxylate-based MOF glass, converted from a crystalline MOF through the liquid phase before decomposition during the heating process. This Account aims to introduce six studies, including the aforementioned example, on the synthesis of CP/MOF glasses from carboxylate-based CPs/MOFs that have been published so far. To overcome the challenges with aromatic carboxylates in CP/MOF glass formation, the metal coordination sphere should be altered and the degree of freedom in the ligands should be increased. Based on these approaches, the strategies for vitrification of carboxylate-based CPs/MOFs can be divided into two categories: desolvation and melt-quenching. Desolvation can be preceded by vapor perturbation such as hydration. Carboxylate-based CP/MOF glasses possess the potential to expand into a broader range of applications beyond those of existing CP/MOF glasses. Alongside the diversity offered by carboxylic acid ligands, these materials mirror the extensive range of applications previously explored in the existing carboxylate-based CP/MOF crystals. Moreover, their high processability, inherent to glass materials, enables their applications in various industrial fields. This versatility may extend to previously unexplored areas of utilization such as a novel class of bioactive glass.