This work describes design of a series of new paddle-wheel binuclear clusters containing twodimensional (2-D) coordination polymers based on ditopic carboxylate linkers, 1,4-benzenedicarboxylate (BDC) or 2-amino,1,4-benzenedicarboxylate (Am-BDC). The strategic use of strongly coordinating base/solvent as blocking ligand to restrict the structure in 2-D space is explored and the role of organic base on the overall structure formation is further elaborated. The isostructural [Zn(BDC)(Py)] n (1) and [Co(BDC(Py)] n (2) were formed by the use of strong base pyridine (Py) as a blocking ligand whereas reaction using N-methylimidazole (Mim) in place of pyridine gives [Co(BDC)(Mim)] n (3) with similar topology and coordination environment. The use of weak/noncoordinating base such as 2-chloropyrimidine, pyrazine and tetramethylammoniumhexafluorophosphate [(CH 3 ) 4 N(PF 6 )] gives the DMF coordinated 2-D frameworks, [Cu(BDC)(DMF)] n (4), [Zn(BDC)(DMF)] n (5) and [Zn(AmBDC)(DMF)] n (6). All the structures crystallize in monoclinic crystal system yielding 2-D nets with square grid 4 4 topology and solid state 3-D structure via extensive non-covalent supramolecular interactions. Surface area analysis via N 2 adsorption of three representative 2-D coordination polymers, 1, 4and 6, indicate that 4 has a surface area of 450 m 2 /g, which is a signature of microporosity while 1 and 6 have moderate (161.6 m 2 /g) and negligible (33 m 2 /g) surface area, respectively.