Porosity Control in Pillar-Layered MOF Architectures: Hydrogen Bonding in Amino-Functionalized 2D Layers

Abstract

Based on crystal engineering, three Zn/Cd-based metal-organic frameworks (MOFs) (FUM-153(Zn-H), FUM-167(Cd-H), and FUM-176(Cd-NH2)) were successfully prepared from the rigid O-donor/flexible N-donor linkers (H2bdc (terephthalic acid) (L(O)H) or NH2-H2bdc (2-Aminoterephthalic acid) (L(O)NH2) and bpfb (N, N'-1,4-(phenylene) diisonicotinamide) (L(N))) with Zn/Cd ions. Structurally, the major difference among the FUMs is the various behaviors of the DMF solvent in the lattice or the coordination environment of the structures. This study investigated the effect of hydrogen bonding of NH2 substitution in 2D layer linkers and its effect on the layer architecture. The results showed that hydrogen bonding indirectly affects the coordination of DMF solvent to the metal center and the porosity. To investigate the effect of the substitution NH2 in the presence or absence of the DMF solvent in the FUMs, the Cambridge Structural Database (CSD) was surveyed for similar structures with the L(O)H and L(O)NH2 linkers. Remarkably, the obtained data suggested that the existence of NH2 substitution may reduce the probability of the coordination of DMF to the metal centers. Theoretical studies were carried out to explore the gas adsorption performance of the titled FUMs. A better CH4 adsorption compared to CO2 for all FUMs was observed. It is worth saying that CH4 and CO2 gas adsorption in FUM-176(Cd-NH2) are higher than FUM-153(Zn-H) and FUM-167(Cd-H). It can be deduced that the NH2 substitution in 2D layer linkers prevented the entering of DMF molecules into the framework (lattice or coordinated solvent). Consequently, more accessible pores are provided for gas molecules. The work demonstrates the role of linker functionality in the crystal structures, pore size, and gas adsorption properties.