Proton Conducting Metal-Organic Frameworks (MOFs) via Post Synthetic Transmetallation and Water Induced Structural Transformations.

Post Synthetic Modification (PSM) of Metal-Organic Frameworks (MOFs) is a crucial strategy for developing new MOFs with enhanced functional properties compared to their parent one. PSM can be accomplished through various methods:1) modification of organic linkers; 2) exchange of metal ions or nodes; and 3) inclusion or exchange of solvent/guest molecules. Herein, PSM of bimetallic and monometallic MOFs containing biphenyl dinitro-tetra-carboxylates (NCA) are demonstrated. The tetra carboxylate NCA, produces monometallic Cd-MOF-1 and Cu-MOF-1 and bimetallic CoZn-MOF in solvothermal reactions with the corresponding metal salts. The CoZn-MOF undergoes post-synthetic transmetallation with Cd(NO) and Cu(NO) in aqueous solution to yield Cd-MOF-2 and Cu-MOF-2, respectively. Additionally, green crystals of Cu-MOF-1 found to undergo a single-crystal-to-single-crystal (SCSC) transformation to blue crystals of Cu-MOF-3 upon dipped into water at room temperature. These MOFs demonstrate notable proton conductivities ranging from 10 to 10 S cm under variable temperatures and humidity levels. Among them, Cu-MOF-3 achieves the highest proton conductivity of 1.36×10 S cm at 90 °C and 98 % relative humidity, attributed to its continuous and extensive hydrogen bonding network, which provides effective proton conduction pathways within the MOF. This work highlights a convenient strategy for designing proton-conducting MOFs via post-synthetic modification.