Two new three-dimensional porous Zn(II)-based metal −organic frameworks, containing azine-functionalized pores, have been readily and quickly isolated via mechanosynthesis, by using a nonlinear dicarboxylate and linear N-donor ligands. The use of nonfunctionalized and methyl-functionalized N-donor ligands has led to the formation of frameworks with different topologies and metal−ligand connectivities and therefore different pore sizes and accessible volumes. Despite this, both metal −organic frameworks (MOFs) possess comparable BET surface areas and CO 2 uptakes at 273 and 298 K at 1 bar. The network with narrow and interconnected pores in three dimensions shows greater affinity for CO 2 compared to the network with one-dimensional and relatively large pores attributable to the more effective interactions with the azine groups.