A variety of network structures have been prepared by transmetalation of a polymer {Na-3[Na-9(Cbdcp)(6)(H2O)(18)]}(n) (1) (Cbdcp = N-(4-carboxybenzyl)-(3,5-dicarboxyl)pyridinium) containing dodecahedral Na-9 aggregate secondary building units with Cu(II) by modulating the temperature, solvent, and pH. These complexes include a large, zwitterionic hexa-cuprometallocycle [Cu-6(Cbdcp)(6)(H2O)(18)] (2) formed in H2O at room temperature, two three-dimensional polymers [Cu-3(Cbdcp)(2)(OH)(2)(H2O)(2)](n) (3) and {[Cu-3(Cbdcp)(2)(OH)(2)]center dot 2H(2)O}(n) (4) isolated from H2O and DMF/H2O at 135 degrees C, and a mononuclear complex [Cu(HCbdcp)(2)(H2O)(3)]center dot H2O (5) from H2O at 100 degrees C and pH = 6. All the complexes are robust and water stable. The crystal framework of macrocycle 2 is stable up to 100 degrees C under vacuum and selectively adsorbs CO2.