A self-assembly of AgClO4 with a Schiff-base ligand N,N'-bis(pyridin-2-ylmethylene)benzene-1,4-diamine (1) gave a 1D zigzag polymeric array [{Ag-2(C18H14N4)(2)}(ClO4)(2)(CH3CN)](n) (3), while the self-assembly of AgClO4 with 3,3'-dimethyl-N,N'-bis(pyridin-2-ylmethylene)biphenyl-4,4'-diamine (2) afforded the molecular rectangle [{Ag-2(C26H22N4)(2)}-(ClO4)(2)] (4). The structures of 3 and 4 were characterized by single-crystal X-ray diffraction analysis. Structural data for 3 indicate that the Ag(l) ion is coordinated by two ligands of 1 in a distorted tetrahedral fashion thereby leading to a 1 D zigzag polymeric array. The zigzag chains are interdigitated with weak pi-pi stacking interactions. The structure of 4 consists of a discrete molecular rectangle where the silver atom has a distorted square-planar coordination with the pyridyl ligands and azomethine nitrogen atoms of 2. An intramolecular pi-pi interaction between the phenyl rings of adjacent Schiff-base 2 functions to stabilize the rectangular architecture. The Ag(l)-Schiff-base coordination polymer 3 is not stable in solution. The degradation and reorganization of 3 to form a [2 x 2] grid architecture [{Ag-4(C26H22N4)(4)} (ClO4)(4)] (3g) was supported in a FAB-MS study. The rectangular structure of 4 remains intact in solution at ambient temperature. The complexes 3g and 4 exhibit unusual luminescence behavior in solution at room temperature with significantly red-shifted emission in the visible region.