Five new silver(I) complexes of the formula [Ag(L-1)(NO3)](n) (1), [Ag-4(L-2)(6)(NO3)(4)] (2), [Ag(L-3)(NO3)](n) (3), [Ag-3(L-4)(3)(NO3)(3)](n) (4), and [Ag(L-4)(NO3)](n) (5) have been synthesized by reactions of silver(I) nitrate with a family of 2-aminopyrimidine and its derivatives (namely, 2-aminopyrimidine (L-1), 2-amino-4,6-dimethylpyrimidine (L-2),2-amino-4-methoxy-6-methylpyrimidine (L-3), and 2-amino-4,6-dimethoxypyrimidine (L-4), respectively). The influences of substituted groups of ligands and reaction solvent systems on the structure of the complexes are discussed. The reaction of AgNO3 with L, yields a one-dimensional (1-D) zigzag chain (1). The reaction of AgNO3 with L-2 leads to a zero-dimensional (0-D) tetramer (2). When L-3 is used, a two-dimensional (2-D) grid network (3) is obtained. On the other hand, by using the same silver(I) nitrate but different reaction solvent systems, 4 and 5 are isolated, respectively. Complex 4 has a 1-D polymeric ribbon further connected by intermolecular hydrogen bonds to form a 2-D layer structure. While 5 shows a 2-D honeycomb-like layer consisting of 24-membered metallocycles. The results reveal that the nature of organic ligands and the choice of solvent all have great impact on the structure of the complexes. In addition, the secondary forces such as hydrogen-bonding interactions including intramolecular and intermolecular hydrogen bonds also play important roles in the formation of supramolecular architectures, for instance, to link low-dimensional entities to high-dimensional frameworks. The luminescence properties of the synthesized silver complexes were investigated in the solid state at room temperature. (C) 2008 Elsevier Ltd. All rights reserved.