Structuralization of Ca²⁺-Based Metal-Organic Frameworks Prepared via Coordination Replication of Calcium Carbonate

The emergence of metal-organic frameworks (MOFs) as potential candidates to supplant existing adsorbent types in real-world applications has led to an explosive growth in the number of compounds available to researchers, as well as in the diversity of the metal salts and organic linkers from which they are derived. In this context, the use of carbonate-based precursors as metal sources is of interest due to their abundance in mineral deposits and their reaction chemistry with acids, resulting in just water and carbon dioxide as side products. Here, we have explored the use of calcium carbonate as a metal source and demonstrate its versatility as a precursor to several known frameworks, as well as a new flexible compound based on the 2,5-dihydroxybenzoquinone (H₂dhbq) linker, Ca(dhbq)(H₂O)₂. Furthermore, inspired by the ubiquity and unique structures of biomineralized forms of calcium carbonate, we also present examples of the preparation of superstructures of Ca-based MOFs via the coordination replication technique. In all, the results confirm the suitability of carbonate-based metal sources for the preparation of MOFs and further expand upon the growing scope of coordination replication as a convenient strategy for the preparation of structuralized materials.