The potential of thio and seleno germanones [LPhGe=E] (L = aminotroponiminate (ATI) ligand, E = S 3, Se 4) to function as ligands has been demonstrated through the isolation of their silver(I) iodide complexes [{(t-Bu)(2)ATIGe(E)-Ph)(2)(Ag2I2)] (E = S 5, Se 6) with a planar and discrete Ag2I2 core. Compounds 5 and 6 possess the hitherto unknown Ge=E -> Ag-I moieties and the crystallographic data reveals the presence of a strong argentophilic interaction (2.950(1) angstrom) in complex 6, but is inconclusive in complex 5 (3.470(1) angstrom). Using theoretical studies, proof for the presence and absence of argentophilic interactions in complexes 6 and 5 was obtained, respectively. Further, it is disclosed that the donor ability of the chalcogen atoms in the Ge=E -> Ag-I moieties dictate the Ag center dot center dot center dot Ag interaction in these complexes.