Optimizing Fe‐Based Metal‐Organic Frameworks through Ligand Conformation Regulation for Efficient Dye Adsorption and C2H2/CO2 Separation

Regulating the structure of metal-organic frameworks (MOFs) by adjusting the ligands reasonably is expected to enhance the interaction of MOFs on special molecules/ions, which has significant application value for the selective adsorption of guest molecules. Herein, two tricarboxylic ligands H3 L-Cl and H3 L-NH2 were designed and synthesized based on the ligand H3 TTCA by replacing part of the benzene rings with C=C bonds and modifying the chlorine and amino groups on the 4-position of the benzene ring. Two 3D Fe-MOFs (UPC-60-Cl and UPC-60-NH2 ) with the new topology types were constructed. As the C=C bonds of the ligands have flexible torsion angles, UPC-60-Cl features three types of irregular 2D channels, while UPC-60-NH2 has a cage with two types of windows on the surface. The synergistic effect of unique channels and modification of functional groups endows UPC-60-Cl and UPC-60-NH2 with high adsorption capacity for organic dyes. Compound UPC-60-Cl shows high adsorption capacity for CV (147.2 mg g-1 ), RHB (100.3 mg g-1 ), and MO (220.9 mg g-1 ), whereas UPC-60-NH2 exhibits selective adsorption of MO (158.7 mg g-1 ). Meanwhile, based on the diverse pore structure and modification of active sites, UPC-60-Cl and UPC-60-NH2 show the selective separation of equimolar C2 H2 /CO2 . Therefore, reasonable regulation of organic ligands plays a significant role in guiding the structure diversification and performance improvement of MOFs.