Synthesis and reactivity of transition metal compounds bearing \"naked\" pnictogen atoms is an active research area with remarkable bonding patterns observed in the formed compounds. Within this field, intense investigations on the coordination behavior of complexes possessing Pn and Asn (2≤n≤5) moieties have been conducted. However, studies on heavier analogues have been ignored so far due to arduous challenges related to low yields and moderate air stability. Herein, we present the first in-depth study addressing the reactivity of organometallic complexes containing Sb-donor atoms with several AgI salts. These reactions afforded twelve unprecedented aggregates as monomers, dimers as well as three- and four-membered chains of AgI ions claimed in the literature to be inaccessible. Interatomic distances as well as computational evidence obtained with help of several different methods suggest the presence of Ag⋅⋅⋅Ag interactions in all complexes containing more than one AgI ion.