A 1 : 3 molar reaction of YI3 and AgI in dimethylformamide (DMF) in the presence of NH4I afforded [Y(DMF)8][Ag3(mu3-I)(mu-I)3I2] (1) with good yield, whereas the similar reaction in dimethylsulfoxide (DMSO) gave complexes [Y(DMSO)8][Ag2(mu-I)3I2] (2) and/or [Y(DMSO)8]2[Ag4(mu3-I)2(mu-I)4I2][I]2 (3), depending on the reaction and crystallization conditions. These discrete heterometallic hybrid compounds 1-3 undergo solid- and solution-state transformations via condensation of iodoargentate anions. So in the confined and solvent-free environment of paratone, crystals of 1 transformed into a 1D zig-zag structure [Y(DMF)8]3+[Ag6(mu4-I)2(mu3-I)2(mu-I)5]1infinity(3-) (4), whereas those of 2 were first converted into 3 and finally into [Y(DMSO)7]4[Ag4(mu3-I)4I4]3 (5). In solution phase, re-crystalization of 1 or 2 from DMSO-toluene gave 3 as an exclusive species, whereas reaction of 1 with 3 equiv of AgI in DMF afforded 4 with good yield. Alternatively, 4 could also be synthesized with excellent yield from a 1 : 6 molar reaction of YI3 and AgI. The above transformations suggest that, for a given metal-organic cation, an iodometallate cluster with higher nuclearity is thermodynamically more stable. Single crystal X-ray structures are reported for all the compounds and a mechanism for the structural transformation of 2 to 3 is proposed. In addition, spectroscopic, thermo-gravimetric and luminescent properties of the complexes 1, 3 and 4, which were obtained exclusively and in pure form, are also described.