Two unusual d(10) compounds, [Zn-2(bipy)(3)(H2O)(8)(ClO4)(2)(paba)(2)]center dot 2(bipy)center dot 4H(2)O (1) and [Cd-2(bipy)(4)(H2O)(6)(ClO4)(2)(paba)(2)]center dot (bipy) center dot 5H(2)O (2) (bipy = 4,4'-bipyridine, paba = p-aminobenzoate), were obtained from reaction of the metal salts, bipy and paba in an EtOH/H2O mixture. The bipy ligands in the two compounds exhibit two new modes of coordinating to transition metal ions, resulting in the formation of large porous frameworks. Immersion of single crystals of 1 in an aqueous solution of NH4PF6 results in the formation of its hexafluorophosphate derivative 3 as shown by single crystal diffraction. Immersion of crystals of 3 in NaClO4 regenerates 1. Furthermore, compound 1 also shows interesting anion sensing properties in an EtOH/H2O mixture.