Self-assembly of AgNO3 with the semirigid tetratopic ligands 1,2,4,5-tetrakis(benzoimidazol-1-ylmethyl)benzene (TBim) and 1,2,4 5-tetrakis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene (TDMBim) afforded compounds [Ag-4(mu(4)-TBim)(2)(mu(2)-eta(2)-NO3)(2)](NO3)(2)center dot 1/2CH(2)Cl(2)center dot 2CH(3)OH (1 mu 1/2CH(2)Cl(2)center dot 2CH(3)OH) and [(NO3-)subset of{Ag-4(mu(4)-TDMBim)(2)}][Ag(NO3)(2)](NO3)(2)center dot CH2Cl2 center dot CH3OH center dot 4H(2)O(2 center dot CH2Cl2 center dot CH3OH center dot 4H(2)O), respectively. The structures of 1 and 2 were characterized by single-crystal X-ray diffraction analysis. Both compounds adopt a M4L2-type tetragonal metalloprismatic cage structure, [Ag-4(mu(4)-L)(2)](4+), with strong intramolecular silver-silver contacts. Compound 1 is a discrete species, while compound 2 is a novel infinite chainlike supramolecular array involving silver metal strings assembled from a [Ag-4(mu(4)-L)(2)](4+) nanocage and silver linkages. Thermogravimetric analyses of 1 center dot 1/2CH(2)Cl(2)center dot 2CH(3)OH and 2 center dot CH3OH center dot 4H(2)O indicate that the Ag4L2-cage structures of 1 and 2 both are thermally stable up to 330 degrees C. Results from an in situ H-1 NMR study of AgNO3 and TDMBim in different molar ratios unambiguously revealed the successive self-organization process, in which self-organization of the molecular cage takes place initially followed by crystallization of the corresponding supramolecular arrays with silver metal strings.