Self-assembly reaction of H(3)btc (1,3,5-benzenetricarboxylic acid), H(2)ta (1,4-benzenedicarboxylic acid) or 1,2,4,5-benzenetetracarboxylic dianhydride with Ag(NO3) in mixed H2O/MeOH solution at room temperature gave rise to four novel 3D polymeric silver(I) complexes. [{Ag(H(2)bTC)}{Ag-2(Hbtc)}](n) (1), [Ag(ta)(1/2)](n) (2), [Ag-2(btec)(1/2)](n) (3) and [(Ag-3(btec)(3/4)}{Ag(H2O)(2)(btec)(1/4))](n) (4) (H(4)btec= 1,2,4,5-benzenetetracarboxylic acid). Complex 1 crystallizes in orthorhombic space group Fddd, with a = 14.877(5), b = 25.926(1). c = 36.377(7) Angstrom, Z = 32. Complex 2 crystallizes in monoclinic space group P2(1)/c, with a = 7.257(6), b = 8.949(8), c = 6.346(5) Angstrom. beta = 111.654(3)degrees, Z = 4. Complex 3 crystallizes in orthorhombic space group P2(1)/c, with a = 8.333(8), b = 6.335(5), c = 10.964(9) Angstrom. Z = 4, whereas complex 4 crystallizes in triclinic space group P (l) over bar, with a = 7.509(1), b = 9.351(1), c = 10.307(7) Angstrom, alpha = 69.514(2), beta = 84.521(2), gamma = 83.638(2)degrees, Z = 2. All compounds possess 3D framework and short Ag-Ag contacts are present in 1-4. In 1, the ligand unsupported Ag-Ag interactions play an important role in the formation of the complex, which is constructed by silver chains formed by Ag-Ag interactions and carboxylate spacers. (C) 2003 Elsevier B.V. All rights reserved.