Advancing Pore-Space-Partitioned Metal-Organic Frameworks with Isoreticular Cluster Concept

Area of Science:

• Inorganic Chemistry
• Materials Science
• Nanotechnology

Background:

• Trigonal planar M3(O/OH) trimers are fundamental building blocks in inorganic chemistry and Metal-Organic Framework (MOF) platforms.
• Advancing isoreticular chemistry requires novel cluster combinations and hierarchical assembly strategies.

Purpose of the Study:

• To introduce and demonstrate the concept of an isoreticular cluster series.
• To synthesize a new series of pore-space-partitioned MOFs (M3M6 pacs) through co-assembly of single-deck and double-deck trimers.
• To explore the gas adsorption and electrocatalytic properties of these novel MOFs.

Main Methods:

• Concept of isoreticular cluster series introduced.
• Co-assembly of M3 single-deck trimer and M3x2 double-deck trimer to form M3M6 pacs.
• Identification of key factors for module optimization and phase selection in MOF synthesis.

Main Results:

• A new isoreticular series of M3M6 pacs MOFs was successfully synthesized.
• Phase selection was achieved, overcoming the formation of previously observed same-cluster phases.
• The M3M6 pacs materials exhibit high surface area, high CO2 and hydrocarbon uptake, and selective adsorption for C2H2/CO2 and C2H2/C2H4 mixtures.
• The materials also demonstrate high-activity electrocatalytic properties.

Conclusions:

• The isoreticular cluster series concept enables the design of advanced, multi-modular MOFs.
• M3M6 pacs represent a new class of MOFs with significant potential in gas storage, separation, and catalysis.
• Optimization of modular components is crucial for controlling MOF phase formation and properties.