The synthesis of stable porous materials with appropriate pore size and shape for desired applications remains challenging. In this work a combined experimental/computational approach has been undertaken to tune the stability under various conditions and the adsorption behavior of a series of MOFs by subtle control of both the nature of the metal center (Co2+, Cu2+, and Zn2+) and the pore surface by the functionalization of the organic linkers with amido and N-oxide groups. In this context, six isoreticular MOFs based on T-shaped ligands and paddle-wheel units with ScD0.33 topology have been synthesized. Their stabilities have been systematically investigated along with their ability to adsorb a wide range of gases (N-2, CO2, CH4, CO, H-2, light hydrocarbons (C-1-C-4)) and vapors (alcohols and water). This study has revealed that the MOF frameworks based on Cu2+ are more stable than their Co2+ and Zn2+ analogues, and that the N-oxide ligand endows the MOFs with a higher affinity for CO2 leading to excellent selectivity for this gas over other species.22451614716156973 Program [2012CB821701]NSFC [91222201, 21573291]STP Project of Guangzhou [201504010031]NSF of Guangdong Province [S2013030013474]