Metal–organic frameworks are a rapidly expanding family of crystalline porous materials and have shown great promise to address various challenges such as gas storage and separation due to their well-defined pore size and unprecedented tunability in both composition and pore geometry. Here, we have synthesized and structurally characterized a number of new metal- organic framework materials and studied the effects of ligands and metal types on the construction and properties of metal–organic frameworks. To probe the effects of functional groups on ligands, two zinc-based three-dimensional frameworks have been synthesized. They consist of zinc-triazolate layers pillared by dicarboxylates with different functional groups. In addition, a very unusual magnesium metal-organic framework material has been made. It consists of novel magnesium acetate chains crosslinked by 1,4-benzenedicarboxylate into a three-dimensional framework with large channels. The phase purity and structures of these materials have been determined by powder and single-crystal X-ray diffraction. Their thermal stability and sorption a properties for gas molecules such as N ₂, H₂, and CO₂ have also been studied.