Herein, we used the 4-fluoro-[1,1′-biphenyl]-3,4′,5-tricarboxylic acid (H3fbptc) ligand to design and construct a new metal–organic framework (MOF), [Cu3(fbptc)2(H2O)3]·3NMP (1), which possesses rich accessible metal sites and F functional groups in the porous walls and shows high uptake for C2H2 (119.3 cm3 g–1) and significant adsorption selectivity for C2H2 over CH4 (14.4) and CO2 (3.6) at 298 K and 100 kPa. In particular, for the gas mixtures of C2H2–CH4 and C2H2–CO2, the MOF reveals large breakthrough time ratios (C2H2/CH4 = 13, C2H2/CO2 = 5.9), which are particularly prominent in dynamic breakthrough experiments, also confirming the excellent potential for the practical separation of C2H2 from two-component mixtures (C2H2–CH4 and C2H2–CO2) and even three-component mixtures (C2H2–CO2–CH4).

Two novel complexes, namely [Cd(L)(NO 3 ) 2 ] n (1) and {[Cd(L)(NO 3 ) 2 ](CH 3 CH 2 OH)} n (2) (L = 1,3,5-tris[1-(4-oxidroxypyridinium-methylene)]benzene) are synthesized solvothermally in different solvents. Single crystal and powder X-ray diffraction, infrared spectroscopy, thermogravimetry, 2D fingerprint plots, and Hirshfeld surface analyses are carried out for these complexes and their topology and thermal stability are also analyzed. Two complexes exhibit the same 2D interpenetrating structure formed by the ligand coordinated with Cd(II) ions. Due to the presence of ethanol molecules in complex 2, part of π⋯π stacking in complex 1 is blocked, resulting in new C-H⋯π and hydrogen bonding. This change makes the weak force stronger and forms a more stable framework. The result is that the thermal stability of 2 is higher than that of 1.