Tunable Metal-Organic Frameworks Based on 8-Connected Metal Trimers for High Ethane Uptake

Metal trimers [M₃ (O/OH)](OOCR)₆ are among the most important structural building blocks. From these trimers, a great success has been achieved in the design of 6- or 9-connected framework materials with various topological features and outstanding gas-sorption properties. In comparison, 8-connected trimer-based metal-organic frameworks (MOFs) are rare. Given multiple competitive pathways for the formation of 6- or 9-connected frameworks, it remains challenging to identify synthetic or structural parameters that can be used to direct the self-assembly process toward trimer-based 8-connected materials. Here, a viable strategy called angle bending modulation is revealed for creating a prototypical MOF type based on 8-connected M₃ (OH)(OOCR)₅ (Py-R)₃ trimers (M = Zn, Co, Fe). As a proof of concept, six members in this family are synthesized using three types of ligands (CPM-80, -81, and -82). These materials do not possess open-metal sites and show excellent uptake capacity for various hydrocarbon gas molecules and inverse C₂ H₆ /C₂ H₄ selectivity. CPM-81-Co, made from 2,5-furandicarboxylate and isonicotinate, features selectivity of 1.80 with high uptake capacity for ethane (123 cm³ g^-1 ) and ethylene (113 cm³ g^-1 ) at 298 K and 1 bar.